Key information

Title
Battery separator and method of manufacturing
Application number
20240223
Case type
National
Status
09.02.2026 Patent meddelt (B1)
Filed
08.03.2024
Effective date
08.03.2024
Publicly available
09.09.2025
Next annual fee due
31.03.2027
Applicant
ZNL ENERGY AS (NO)
Owner
ZNL ENERGY AS (NO)
Inventor
Jan Børge Sagmo (NO) et al.
Agent
HÅMSØ PATENTBYRÅ AS (NO)
Granted
09.02.2026
Patent number
349508
Expiry date
08.03.2044

Abstract and drawing

Disclaimer: This text has been machine-scanned and may contain errors – please refer to "Publications" for legally binding content.
There is disclosed a solid state separator for battery, the solid state separator comprising: - a first layer including a pre-lithiated or presodiated polyphenylene sulfide (PPS) cellulose nanofibre (CelNF) composite free-standing film; - a second layer including a porous polyolefin film; and - a third layer including a ceramic nanolayer provided in-between the first and second layers. There is also disclosed a battery including such a separator as well as methods and a system for production their production.

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 12.02.2026 09-01 Saksbehandling 20240223(349508) UT PT Registreringsbrev nasjonal patent (15) (PT20240223)
02.02.2026 08-01 Saksbehandling 20240223 UT PT Varsel om betaling av første årsavgift (3317) (PT20240223) HÅMSØ PATENTBYRÅ AS
 24.11.2025 07-01 Saksbehandling 20240223 UT Intention to grant HÅMSØ PATENTBYRÅ AS
 08.09.2025 06-05 Saksbehandling 20240223 INN P31227NO00_response letter HÅMSØ PATENTBYRÅ AS
 08.09.2025 06-04 Saksbehandling 20240223 INN P31227NO00_norske krav HÅMSØ PATENTBYRÅ AS
 08.09.2025 06-03 Saksbehandling 20240223 INN P31227NO00_corrected claims_MU HÅMSØ PATENTBYRÅ AS
 08.09.2025 06-02 Saksbehandling 20240223 INN P31227NO00_corrected claims_clean HÅMSØ PATENTBYRÅ AS
 08.09.2025 06-01 Saksbehandling 20240223 INN Korrespondanse (Hovedbrev inn) HÅMSØ PATENTBYRÅ AS
 15.08.2025 05-01 Saksbehandling 20240223 UT Substantive Examination HÅMSØ PATENTBYRÅ AS
 01.04.2025 04-04 Saksbehandling 20240223 INN P31227NO00 Description and claims - tracked HÅMSØ PATENTBYRÅ AS
 01.04.2025 04-03 Saksbehandling 20240223 INN P31227NO00 Description and claims - clean HÅMSØ PATENTBYRÅ AS
 01.04.2025 04-02 Saksbehandling 20240223 INN P31227NO00 Covering letter HÅMSØ PATENTBYRÅ AS
 01.04.2025 04-01 Saksbehandling 20240223 INN Korrespondanse (Hovedbrev inn) HÅMSØ PATENTBYRÅ AS
 04.10.2024 03-02 Saksbehandling 20240223 UT PT report 01:42:53
04.10.2024 03-01 Saksbehandling 20240223 UT Substantive Examination HÅMSØ PATENTBYRÅ AS
 11.03.2024 02-01 Saksbehandling 20240223 UT Informasjon til oppfinner De Chen
 08.03.2024 01-04 Saksbehandling 20240223 INN P31227NO00_fig 1074803 HÅMSØ PATENTBYRÅ AS
 08.03.2024 01-03 Saksbehandling 20240223 INN P31227NO00_description and claims HÅMSØ PATENTBYRÅ AS
 08.03.2024 01-02 Saksbehandling 20240223 INN P31227NO00 General Power of Attorney HÅMSØ PATENTBYRÅ AS
 08.03.2024 01-01 Saksbehandling 20240223 INN Søknadsskjema Patent HÅMSØ PATENTBYRÅ AS

Description, claims and drawings

Disclaimer: This text has been machine-scanned and may contain errors – please refer to "Publications" for legally binding content. Description
3495081BATTERY SEPARATOR AND METHOD OF MANUFACTURINGThe invention relates to a solid state separator for a battery. More specifically, the invention relates to a solid state separator including a pre-lithiated or presodiated polyphenylene sulfide (PPS) cellulose nanofibre composite free-5 standing film as well as a battery including such as separator. The invention also relates to a system and methods of producing a PPS cellulose nanofibre composite free-standing film.The development of advanced separators holds the key to significantly enhancing the safety of batteries. Separators act as critical components within 10 metal ion batteries such as Lithium (Li), Sodium (Na), and Zinc (Zn), preventing physical contact between the anode and cathode, which could lead to short circuits and thermal runaway. Innovations in separator technology, such as improved thermal stability, enhanced electrolyte compatibility, and the incorporation of flame-retardant materials, are pivotal in reducing the risk of bat-15 tery failures. By focusing on the advancement of safer and more reliable separators, the battery industry can address the inherent safety concerns of lithium- and sodium-ion batteries, paving the way for their wider and more secure application across various sectors, including consumer electronics and electric vehicles.20 Solid separators are vital for the safety, efficiency, and performance of Li and Na ion batteries. Originally, these batteries used porous polymers like polyethylene and polypropylene as separators, selected for their capability to enable ionic conductivity through electrolyte-filled pores and to maintain a physical barrier between the anode and cathode, thus preventing short circuits. How-25 ever, these porous separators presented notable issues. They could lead to nonuniform lithium ion transport and create localized electrical fields that may encourage the formation of lithium dendrites, particularly around the pores. Additionally, their tendency to shrink under high temperatures could result inP31227NO00 description and claims 3495082short circuits, and their structural integrity was at risk of being compromised by punctures.In response to the limitations of traditional porous separators, there has been a notable trend towards the development of non-porous solid separators in 5 lithium-ion batteries. Unlike their microporous counterparts, non-porous separators lack any form of pores or openings within their structure. This design is instrumental in curbing the formation of lithium dendrites - sharp, needle-like projections that can emerge on lithium metal anodes. These dendrites pose significant risks, including the potential for short circuits and safety hazards.10 Additionally, their robust structure makes the battery more resistant to physical damages. By integrating non-porous separators, it's possible to enhance both the capacity and energy density of lithium-ion batteries. This improvement is particularly beneficial for devices employing lithium metal anodes, including wearable technology, drones, and electric vehicles, where performance 15 and safety are paramount. These advanced separators offer improved thermal stability and mechanical strength at high temperatures, greatly enhancing battery safety.However, the transition to non-porous materials requires overcoming several challenges, including the development of new solid electrolytes that can con-20 duct lithium ions without liquid electrolytes and scalability to large-scale production. These materials must possess high ionic conductivity, electrochemical stability, and compatibility with electrode materials. Moreover, adapting manufacturing processes to accommodate these new materials and ensuring scalability for mass production are essential steps for the widespread adoption of 25 non-porous separators in lithium-ion batteries.Transitioning to non-porous materials for lithium-ion batteries involves navigating through a set of complex challenges. Key among these is the innovation of new solid electrolytes capable of facilitating lithium ion movement without the need for traditional liquid electrolytes. These novel materials must exhibit 30 exceptional ionic conductivity, maintain electrochemical stability, and be fully compatible with existing electrode materials. Additionally, the manufacturing processes must evolve to integrate these advanced materials effectively, en-P31227NO00 description and claims 3495083suring that they can be produced at scale. Achieving scalability for mass production is crucial to enable the broad implementation of non-porous separators in the Li- and Na-ion battery industries.The solid separator made by pre-lithiated polyphenylene sulfide (PPS) has 5 shown promising properties such as high Li ion conductivity, thermal stability, and chemical resistance (US2022037696), owning to PPS is a highperformance thermoplastic polymer known for its exceptional resistance to heat, chemicals, and corrosion, as well as its rigidity and dimensional stability. However, due to its stiffness, it is difficult to process it to thin film. The thin 10 film has relatively low mechanical strength, and mechanical reinforcement is necessary.As research in this area continues to advance, the development of non-porous solid separators is poised to significantly enhance the safety, capacity, and overall performance of Li- and Na-ion batteries. This progress is expected to 15 open new possibilities for their application, ranging from consumer electronics to electric vehicles and energy storage solutions, marking a significant leap forward in battery technology.CN 108878751 B discloses a conductive ceramic composite diaphragm and a solid-state battery. The conductive ceramic composite diaphragm comprises a 20 porous base membrane and a conductive ceramic composite coating layer which is coated on one side or two sides of the porous base membrane, wherein the conductive ceramic composite coating layer comprises the following components based on the total weight thereof: 5-80wt% of an organic polymer, 10-85wt% of a nano inorganic solid electrolyte, 1-20wt% of high-25 molecular grafted modified ceramic, 1-12wt% of a binder and 0.1-0.5wt% of a wetting agent.US 2019/0237731 A1 discloses a porous film, a separator including the porous film, an electrochemical device including the porous film, and a method of preparing the porous film are provided, wherein the porous film includes:30 small-diameter fibers having an average diameter of about 50 nm or less; and large-diameter fibers having an average diameter of about 100 nm or greater, wherein an amount of the large-diameter fibers is about 5 wt % to about 60P31227NO00 description and claims 3495084wt % based on a total weight of the small-diameter fibers and the largediameter fibers.US 2016/0204406 A1 discloses a separator for an electrochemical device, comprising: a porous polymer film; and a porous coating layer formed on one 5 or both surfaces of the porous polymer film and comprising at least one of inorganic particles and organic particles, and a binder polymer, wherein fibrils in the surface of the porous polymer film are entangled with the particles in the porous coating layer in the contact surface between the porous polymer film and the porous coating layer, and the separator has an air permeability of 100 10 to 800 sec/100 cc, an electrical resistance of 0.5 to 1.5Ω, and a heatshrinkage rate of 8% or less in each of machine and transverse directions, and an electrochemical device having the same.The invention has for its object to remedy or to reduce at least one of the drawbacks of the prior art, or at least provide a useful alternative to prior art.15 The object is achieved through features, which are specified in the description below and in the claims that follow.The invention is defined by the independent patent claims. The dependent claims define advantageous embodiments of the invention.In a first aspect, the invention relates to a solid state separator for a battery, 20 the solid state separator comprising:- a first layer including a pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre (CelNF) composite (PPSCC) free-standing film;- a second layer including a porous polyolefin film; and- a third layer including a ceramic nanolayer provided in-between the first and 25 second layers.In one embodiment, the second layer may include polyethylene (PE) or polypropylene (PP). Both PE and PP has been shown to be useful for preventing thermal runaway, enhancing mechanical strength and for suppressing the reduction and oxidation of the first layer of the solid-state battery separator.P31227NO00 description and claims 3495085The second layer may have a thickness in the range in the range 5-20 µm, preferably 5-10 µm. A thin layer is desirable for maintaining a high energy density in batteries, while a thicker layer is desirable for enhanced mechanical stability. 5-20 µm, and in particular 5-10 µm, has been found to be an optimal 5 trade-off in certain applications.In one embodiment, the first layer may include PPS, CelNF, and polytetrafluoroethylene (PTFE) powder with a weight ratio of 89-97%: 0.1-5%: 3-8%, preferably 90-94%: 1-3%: 4-6%, respectively. A smaller fraction of welldispersed CeLNF holding a threshold of fiber network in the separator enhanc-10 es the mechanical properties as well as Li-ion transport, but without generating too many pores in the solid separator. In addition of a small fraction of PTEF, the fibrous structure helps processability to produce free-standing film, but without damaging the ion transport properties of PPS film.In one embodiment, the ceramic nanolayer may have a thickness in the range 15 30-300 nm.The first layer may have a thickness of 5-45 μm, preferably 10-30 μm, and even more preferably 15-25 μm.In one embodiment the first layer may have a porosity lower than 10%, preferably lower than 3%. The porosity may be measured by means of N2 or CO2 20 absorption.The third layer may include one or more of the following:- alumina;- a Li-rich ceramic, such as Li salts, Li rich cathode materials, Lithium Phosphorous Oxynitride (LiPON) or lithium titanate; and25 - a highly porous material, such as carbon nanospheres or metal-organic framework (MOF) materials.Thickness of the separator may be in the range of 10-60 μm, preferably 15-30 μm, and even more preferably 20-25 μm. As for the first layer, the total thickness of the separator is a trade-off between the energy density of the battery 30 in which the separator will be used and its mechanical stability.P31227NO00 description and claims 3495086In one embodiment the solid state separator may have a width in the range of 5 -160 cm, where the upper end of the range may correspond to a width in an industrial-scale process, while lower end of the range may correspond to a typical width in a laboratory-scale process.5 Addressing the challenges identified in previous approaches, this invention introduces a solid separator designed to significantly enhance battery performance. The invention provides a multifunctional solid state separator for batteries, such as Li- or Na-ion batteries, including a multilayer structure. The top layer is the PPS-cellulose nanofibre composite “free standing” film, and the 10 bottom layer is the porous polyolefin, such as PE, layer. Between the two layers is provided a ceramic nanolayer. The solid state separator according to the first aspect of the invention has exceptional mechanical strength while at the same time its method of manufacturing has been significantly simplified.This design ensures excellent compatibility and wettability with electrolytes, 15 facilitating efficient ion transport. Additionally, the separator boasts superior thermal characteristics, with PPS's high melting point of 280-285°C contributing to its robust and stable performance. This feature, combined with the material's ability to prevent thermal runaway, significantly enhances battery safety. This non-porous PPSCC film, i.e. the first layer, is designed to selec-20 tively permit the passage of lithium or sodium ions, thereby reducing dendrite growth. It achieves this by promoting a uniform ion diffusion and eliminating any pores, which effectively halts the formation of lithium dendrites. The composite film is produced from a blend of pre-lithiated polyphenylene sulfide (PPS) powder, cellulose fibres (CelNF), and polytetrafluoroethylene (PTFE) 25 powders, forming a thin, solid membrane separator. The production process, as will be presented in the following, involves orienting and heating the mixture of pre-lithiated or pre-sodiated PPS powder, cellulose fibres, and PTFE in a supersonic dry airflow, subsequently pressing it into a free-standing film with a precisely controlled thickness. During this process, the PTFE is transformed 30 into fibres, and a small amount of cellulose nanofibre, ranging from 0.01 to 3 weight percent, is incorporated into the composite. This addition not only enhances the thermal elongation properties of the thermoplastic PPS powder butP31227NO00 description and claims 3495087also significantly boosts the mechanical strength of the free-standing film, thereby improving the controllability of the automatic manufacturing process. The present disclosure directs the PPSCC film multifunctional. The multilayer designed a thin polyolefin, polyethylene (PE) or polypropene (PP) layer porous 5 layer with a thickness, typically ranging from 3-10 micrometres. It provides the function of thermal runaway prevention: In the case of excessive heat, the pores close and ion transport effectively shuts down with increasing temperature until the PE layer melts at about 105-130°C, and PP layer at 130-170°C. In addition, the PPSCC film has a very good thermal stability and keeps excel-10 lent dimensional stability up to 280 °C, preventing direct contact of the anode and cathode, thus significantly reducing the short circle potential. PPS exhibits a low flammability rate according to the UL94 standard, achieving a V-0 rating. This indicates a high level of fire resistance, providing an additional safety feature. This design prevents the battery from reaching the thermal runaway 15 threshold and potentially venting with flame, thereby enhancing safety.The present disclosure directs the PPSCC film multifunctionality by engineering a coating layer between the PPSCC and polyolefin layer, i.e. the third layer between the first and second layers. The coating layer may e.g. include alumina, Li rich ceramic, such as Li salts, Li rich cathode materials, Lithium Phos-20 phorous Oxynitride (LiPON) and lithium titanate, highly porous materials, such as carbon nanospheres and MOF materials. A solution containing the above materials is used as glue to laminate the polyolefin and PPSCC layer to each other. The third layer formed after drying, such as alumina, increases the dimensional stability of the polyolefin layer. Lithium-rich materials or com-25 pounds, such as Li salts, Li rich cathode materials, Lithium Phosphorous Oxynitride (LiPON), lithium titanate, provide Li supplementation. In lithium batteries, particularly lithium-ion batteries, additional lithium is sometimes introduced to compensate for lithium loss during the initial charging and to enhance overall battery performance. MOF materials in the coating layer may 30 increase the holding of electrolytes and improve the compatibility with electrodes.P31227NO00 description and claims 3495088In a second aspect, the invention relates to a battery including a solid state separator according to the first aspect of the invention.In one embodiment, the battery may be a Li or Na battery.In a third aspect the invention relates to a method for producing a free-5 standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film (PPSCC), the method including the steps of:- mixing and milling metal chloride dissolved in deionized water, tetrachloro-pbenzoquinone (TCBQ) and PPS powder to form a mixed slurry;- transferring the mixed slurry to a reactor for hydrothermal treatment;10 - washing and filtering the hydrothermally treated mixture in a centrifuge;- drying the filtered solution to disintegrate PPS powder;- mixing the disintegrated PPS powder with cellulose fibres and polytetrafluoroethylene (PTFE) powder at a temperature at which the PTFE powder is in a glass state to obtain a mixed solution;15 - griding the mixed solution in dry, compressed air;- compacting the grinded, mixed solution through one or more rollers to obtain a film; and- passing the film through a hot calendering machine to obtain the freestanding, pre-lithiated polyphenylene sulfide (PPS) cellulose nanofibre compo-20 site film.In a fourth aspect, the invention relates to a method for producing a freestanding, pre-lithiated polyphenylene sulfide (PPS) cellulose nanofibre composite film, the method including the steps of:- mixing and milling metal chloride dissolved in deionized water, tetrachloro-p-25 benzoquinone (TCBQ), PPS powder and cellulose fibres to form a mixed slurry;- transferring the mixed slurry to a reactor for hydrothermal treatment;- washing and filtering the hydrothermally treated mixture in a centrifuge; - drying the filtered solution to disintegrate PPS powder;- mixing the disintegrated PPS powder with polytetrafluoroethylene (PTFE) 30 powder at a temperature at which the PTFE powder is in a glassy state to obtain a mixed solution;- griding the mixed solution in dry, compressed air;P31227NO00 description and claims 3495089- compacting the grinded, mixed solution through one or more rollers to obtain a film; and- passing the film through a hot calendering machine to obtain the freestanding, pre-lithiated polyphenylene sulfide (PPS) cellulose nanofibre compo-5 site film.In one embodiment the metal chloride may be one or more of the following: - lithium chloride;- sodium chloride;- magnesium chloride; and10 aluminum chloride.In one embodiment the PPS powder may be a linear chain and end crosslinked semi-crystalline PPS powder, with a degree of crystallinity > 60% in the range 1-25 μm, preferably 1-5 μm.The mass ratio of metal chloride, DIW and TCBQ to the total mass of PPS may 15 be substantially 1:30:5:100.In one embodiment the hydrothermal treatment may be performed at a reaction temperature of approximately 210 °C, for 1-3 hours, preferably around 2 hours, and a vapour pressure of 60-70 bar.In one embodiment, mixing of PPS powder with cellulose fibres and PTFE may 20 takes place at a temperature of 45-50°C.In one embodiment the griding may performed in an air jet mill pre-heated by compressed air to a temperature of 40-50 °C.The step of compacting the grinded, mixed solution through one or more rollers may include producing a film with a thickness of 1.0-3.0 mm, preferably 25 1.0-1.5 mm. In one embodiment, the method may further include the step of passing the film through the hot calendering machine, includes the step of cold-rolling the film at a roller temperature of approximately 40-70 °C, preferably 45-55 °C, to obtain a film with a thickness of 0.3-0.5 mm.P31227NO00 description and claims 34950810In one embodiment the hot calendering machine may have a roller temperature of 125-130°.A friction of the roller may be in the range of 1-20%, preferably 8-12%.The line load may be in the range of 500-250 N/mm, preferably 350-370 5 N/mm.The speed may preferably be 100 m/min or higher when the process is upscaled to an industrial process. Though the experiments presented below, have mainly been done in controlled small-scale set-ups, the speed and line load / roll pressure can be increased without influencing the parameters of the 10 previous steps of the method to any significant degree.In a fifth aspect the invention relates to a method of producing a freestanding, pre-lithiated polyphenylene sulfide (PPS) cellulose nanofibre composite film according to the method of the third or fourth aspects of the invention, the method further comprising the steps of:15 - laminating a film of porous polyolefin to the PPS cellulose nanofibre film by means of a glue including a ceramic nanolayer.In a sixth aspect, the invention relates to a system for carrying out the method according to the third, fourth or fifth aspects of the invention, the system comprising: :20 - primary storage tanks for metal chloride, deionized water, tetrachloro-pbenzoquinone (TCBQ), PPS powder and optionally cellulose fibre,- a first mixer for mixing content from the primary storage tanks into a mixed slurry;- a reactor for hydrothermal treatment of the mixed slurry;25 - a centrifuge for washing and filtering the hydrothermally treated slurry;- means for drying the filtered solution to disintegrate PPS powder;-secondary storage tanks for disintegrated PPS powder, polytetrafluoroethylene (PTFE) powder and optionally cellulose nanofibres (if not included in the primary storage tanks);30 - a second mixer for mixing content from the secondary storage tanks;- a grinder for grinding the mixed solution in compressed air;P31227NO00 description and claims 34950811- one or more pairs of rollers for compacting the grinded solution into a film; - a hot calendaring machine through which the compacted film is passed to obtain a free-standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film; and optionally5 - a laminator to add a film of porous polyolefin to the free-standing, prelithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film by means of a ceramic nanolayer glue to obtain a solid state battery separator.Below follows and exemplary implementation of a method according to the 10 third aspect of the invention in the form of a continuous manufacturing process for the large-scale production of the PPSCC layer of a solid separator disclosed herein. This exemplary process encompasses several stages:a) Mixing of powders to achieve a uniform blend.b) Pre-treating mixed powders in an autoclave reactor, preparing it for 15 subsequent stages.c) Filtering pre-treated, mixed powders using a centrifuge to separate and refine the components.d) Drying the filtered, mixed powders in a fluidized bed reactor for optimal moisture content.20 e) Final, thorough mixing of pre-treated Polyphenylene Sulfide (PPS) powder with celluslose nanofibres and PolyTetraFluoroEthylene (PTFE) powder to ensure even distribution.f) Conveying the final, mixed solution into a high-speed shearing machine using preheated compressed air, with the airflow rate reaching super-25 sonic speeds to fiberize the powder.g) Extruding the fiberized powder through a roller compactor to form pellets.h) Processing the pellets through an automatic multiple rollers machine, which involves sequential cold and hot calendering/rolling steps to final-30 ize the self-supporting PPSCC film.The outcome of this exemplary process is a substantially defect-free, freestanding film with a thickness ranging from 5 to 45 µm, typically 10-30 µm and a width varying between 5 to 160 cm. This innovative manufacturing ap-P31227NO00 description and claims 34950812proach ensures high-quality, consistent production of solid separators suitable for large-scale applications.As used herein, the terms of “lithium battery” and “sodium battery”, refer to all types of Li and Na batteries known as, but not limited to, rechargeable or 5 secondary Li, Na and Zn ion batteries, metal batteries etc.In the following is described an example of an embodiment illustrated in the accompanying drawings, wherein:Fig. 1 shows a schematic system according to the sixth aspect of the invention.10 Any positional indications refer to the position shown in the figures.In the figures, same or corresponding elements are indicated by same reference numerals. For clarity reasons, some elements may in some of the figures be with-out reference numerals.Fig. 1 shows an exemplary and highly schematic system 1 according to the 15 sixth aspect of the invention. The system 1 as shown is adapted to produce a solid state separator according to the first aspect of the invention by means of methods according to the fourth and fifth aspects of the invention.A plurality of storage tanks / dispensing pods is provided, where a first storage tank 2 includes pre-lithiated PPS powder, a second storage 4 tank includes 20 tetrachloro-p-benzoquinone (TCBQ), a third storage tank 6 includes metal chloride (xCl), a fourth storage tank 8 includes deionised water (DIW) and a fifth storage tank 10 includes cellulose nanofibres (CelNF). It should be noted that is this embodiment, the CelNF is added and mixed into the solution from the start, rather than at the later fibrillation step.25 One of more first dispensing pumps 12 are provided to dispense content from the various tanks 2-10 at desired amounts into a first resonance acoustic mixer (RAM) 14, with a not shown grinding medium. The grinding medium may in certain embodiments be Teflon-coated balls, such steel balls, or ceramic balls. A first RAM dispensing pump 15 is provided to move the mixed slurry from theP31227NO00 description and claims 34950813RAM 14 into a closed reactor 16, here in the form of an autoclave, for hydrothermal treatment. The autoclave 16 is provided with not shown means for controlling in- and outfeed. From the autoclave 16, the mixed slurry is further supplied to a peeler centrifuge 18, via an autoclave dispensing pump 17. In 5 the peeler centrifuge 18, the slurry is washed to a neutral pH and filtered to a “cake”. By means of a centrifuge dispensing pump 20, the filtered cake is transferred to fluidized bed reactor 22 to disintegrate agglomerated particles, now in the form on PPS powder with CelNF. Via a fluidized bed dispensing pump 24, the PPS powder with CelNF is fed to a sixth storage tank 26 in which 10 it is mixed with xCl. A seventh storage 28 tank includes PTFE powder. Via cold room dispensing pumps 30, 32 content from the sixth and seventh storage tanks 26, 28, respectively, are sucked into a second RAM 33. The second RAM 33, sixth and seventh storage tanks 26, 28 and the cold room dispensing pumps 30, 32 are provided in a cold room 34, implying that the PTFE powder 15 is in a glassy state.The mixed solution from the second RAM 33 is fed to a jet mill 36 via a second RAM dispensing pump 37, together with compressed air from a rotary screw air compressor 38. The air is pharmaceutical grade dry compressed air according to the standard ISO 8573-1 and class 1-2-1 (particles-water-oil). The rota-20 ry screw air compressor 38 receives air from the fluidized bed reactor via a cooler 40. During the air jet milling process a size reduction of PPS powder particles takes place due to grinding combined with shear forces, whereby PTFE molecular chains extend and open to form fibres. The PTFE fibres form a net-like binding structure on the surface of the PPS particles, giving them a 25 cotton candy-like powder appearance. The cotton candy-like powder is collected by a gas filter.The powder from the air jet mill 36 is dispensed via a jet mill dispensing pump 42 into a screw feeder array 44. The screw feeder array 44 feeds the powder, now in the form strips/ribbons to a sequence of vertical gap-controlled cold 30 rollers at room temperature. In the shown embodiment, the sequence includes three primary pairs of rollers 46 operating in parallel and feeding the resulting film 50 to a secondary pair of rollers 48, generating a film with a thickness in the order of 1 mm. The resultant, rather thick film, is then passed through aP31227NO00 description and claims 34950814plurality of horizontally arranged rollers 52 with gradually reduced gaps between them and at temperature of approximately 50°C. The resulting film after the horizontal rollers has a thickness in the order of 0.5 mm and is substantially free of defects.5 After the horizontal rollers 52, the film 50 is passed to a hot calendaring machine 54 at approximately 130°C. A pressure between rollers 56 of the calendaring machine 56 set to 45 kN, corresponding to a line load of 360N/mm. The friction between the rollers 56 was 10% and the speed 2.5 m/min. Friction is defined as friction in the roller bearings and may be controlled by individually 10 controlling the speed of the rollers 56.The final PPSCC film 50 was then trimmed in an edge trimming machine 57 before a ceramic nanolayer glue, stored in an eight storage tank 58, was applied to the film in a glue applicator machine 60. Glue is dispensed from the eight storage tank 58 by means of a glue dispensing pump 62. The film 50 15 with the glue was then laminated to a PE/PP film 64 in a laminator 66. The PE/PP film 64 is stored on a reel 68. The resultant film 3 passes through a slitting array 70 before it is stored on a storage reel 72 in its desired length and width.The process is executed and controlled from a control unit 74.20 Further examples of methods according to the invention and reference examples are presented in the following. In particular, Examples 1, 3 and 7-8 correspond to methods according to various aspect of the invention, while examples 2, 4-6 and 9 are included for reference.Example 1:25 This embodiment provides a process for fabricating a multifunctional solid Li battery separator, which includes the following steps:(1) Powder mixtureDissolved metal chloride(xCl) in deionized water (DIW), tetrachloro-pbenzoquinone (TCBQ) and polyphenylene sulfide (PPS) powder are mixed andP31227NO00 description and claims 34950815milled in resonance acoustic mixer with grinding medium. The mixed slurry is thereafter transferred into a closed reactor for hydrothermal reaction. After the reaction, the powder is washed to a neutral pH and filtered in vertical peeler centrifuge. The filtered cake is dried in a fluidized bed dryer to disinte-5 grate the agglomerated particles which is then PPS powder.(2) FibrillationPre-lithiated PPS powder, CelNF, and PTFE powder are mixed according to the weight percentage of 91%:3%:6% in a resonance acoustic mixer evenly without shear forces to powder, and the mixing process is carried out under the 10 temperature condition that polytetrafluoroethylene is in a glassy state.The preheated pharmaceutical grade dry compressed air according to the standard ISO 8573-1 and class 1-2-1 (particles-water-oil) from a rotary screw air compressor is injected into a spiral air jet mill.The powder is introduced into the air jet mill grinding chamber through a 15 feeder with high-speed dry compressed air. During the air jet milling process a size reduction of PPS powder particles takes place due to grinding combined with shear forces, whereby PTFE molecular chains extend and open to form fibres. The PTFE fibres form a net-like binding structure on the surface of the PPS particles, giving them a cotton candy-like powder appearance. The cotton 20 candy-like powder is collected by a gas filter.(3) Film making:The powder then enters roller pre-compacters through a feeding mechanism to make thick strips or ribbons. These strips or ribbons are then directly fed into multiple sequential vertical automatic gap-controlled cold rollers at room tem-25 perature to generate a film with a thickness from 1.0 to 1.5mm.The resultant thick film is then passed through the multiple horizontal rollers which is controlled by automatic constant force and speed at a friction of 15% and at a temperature of 50°C. The gaps of the multiple rollers are 1000, 900, 700, 600, and 500 μm, respectively. The thickness of the final defect-free film 30 was 520 μm.P31227NO00 description and claims 34950816The resultant film is passed to hot horizontal calendering which is controlled by a constant force and speed at a friction of 10% temperature of 130° C. The film thickness after the hot calendering was 15 μm. This thickness was obtained with a roll pressure of 45 kN, corresponding line load of 360 N/mm 5 width, and at a speed of 2.5 m/min. When upscaling production, higher speeds should be used, such as in the order of 100 m/min or even higher.The produced separator was then cut into the desired widths and the outer edges were cut off to make a separator including a PPS layer with cellulose nanofibres.10 (4) PE layer LaminationTo make prepare the solid separator for use in Li and Na batteries, a polyolefin layer is attached to the PPS layer to prevent thermal runaway and enhance the mechanical strength.A PE layer or PP layer is laminated to one side of the PPS layer to increase the 15 mechanical strength of the solid separators. The PE layer or PP layer was adhered to the PPS with ceramic glue with alumina colloids. The laminated layer was finally dried in air at a temperature of 120 °C. The ceramic glue becomes a coating layer of Al2O3.The conductivity of lithium ions was determined using a multichannel constant 20 potential instrument (PARSTAT MC, AMETEK), employing electrochemical methods. The measured lithium ion conductivity was found to be 2.5 × 10^-4 S/cm2. The tensile strength of the films was evaluated in accordance with the ASTM D882 standard test method, resulting in a measured tensile strength of 19.4 Mpa.25 The thermal stability of the multilayer film was tested at 130°C. The PE layer was melted, but the PPS layer was kept in its original dimension, Demonstrating its prevention of thermal runaway and thereby increased safety in solid state batteries.The porosity measured by N2 adsorption was 3%. The gas tightness of the 30 film was measured by the ASTM F2622 standard test method. No gas permea-P31227NO00 description and claims 34950817bility was observed. It suggests that the nonporous solid separator is obtained with a small fraction of closed pores.Example 2:All the steps are similar to one in Example 1, except that the fibrillation pro-5 cess only PPS powder and PTFE powder are mixed according to the weight percentage of 94%:6%, i.e. without the cellulose fibers.It has been shown that it is difficult to make a film with a thickness from 1.0 to 1.5 mm by the first step of the film-making process in Example 1. Several times rounds of pre-compacting through a feeding mechanism to make thick 10 strips or ribbons may be useful in that regard.The measured lithium-ion conductivity was found to be 2.1× 10^-4 S/cm^2. The tensile strength was 14.1 Mpa.Example 3:All the steps similar to Example 1, except that in this embodiment there was 15 no PE layer Lamination step whereby the final product includes only the PPSCC freestanding film, without the PE lamination layer. The PPSCC film has a 5.1 Mpa tensile strength, which is much lower than 19.1 Mpa tensile strength of the multilayer structure. This demonstrates the impact of the third and second layers on the tensile strength of the multilayer structure.20 Example 4:All the steps are similar to the ones in Example 2, except that in this embodiment there was no PE layer Lamination, whereby the final product includes only the PPS freestanding film, without the PE lamination layer and without the cellulose nanofibres. The free-standing PPS film without cellulose nanofibre 25 and the PE lamination layer has tensile strength of 0.4 Mpa., The tensile strength is significantly lower than in the previous examples, making the winding of a thin PPS film very difficult.Example 5:P31227NO00 description and claims 34950818All the steps are similar to the ones in Example 2, except that in this:The resultant 520 μm thick film was passed to the hot horizontal calendering which is controlled by a constant force. The average film thickness of 7, 11 and 19 μm was obtained at the roll pressure of 30 kN (rather than 45kN as in 5 Example 2), a friction of 10% at 130° C, and a speed of 0.5, 1.5 and 2.5 m/min, respectively, demonstrating the effect of the roll pressure and speed on the final thickness of the PPS film.Example 6:All the steps are similar to one in Example 2, except that in this:10 The resultant 520 μm film was passed to the hot horizontal calendering which is controlled by a constant gap, in contrast to constant force in the previous Examples A PPS film thickness of 40-50 μm was obtained at the roll gap of 10 μm, A speed of 0.5 m/min, a friction of 10%, and the surface temperature of the roller at 130° C, demonstrating that it may be difficult to make the final 15 PPS film sufficiently thin if controlling by a constant gap instead of force.Example 7:All the steps were similar to the ones in Example 1, except that in this embodiment:The powder entered the powder rollers pre-compacter through a feeding 20 mechanism to make thick strips/ribbons, and these ribbons are then directly fed into multiple sequential vertical automatic gap-controlled rollers at 50 °C, as in Example 1, to generate a thick film ranging from 1.0 to 1.5mm.Pin holes were observed on the final 15 μm after the hot calendering, which demonstrates the importance of performing the pre-compacting at room tem-25 perature.Example 8:All the steps are similar to the ones in Embodiment 1, except that in this embodiment the PPS powder was pre-sodiated:P31227NO00 description and claims 34950819The procedure is similar to Embodiment 1 step 2, except that, in this embodiment, polyphenylene sulfide powder containing 600 ppm of Na, cellulose fibre, and PTFE powder were mixed according to the weight percentage of 91%:3%:6%. The measured porosity was 9%. The pores were filled with 5 NaBF4 electrolytes, and the measured Na ion conductivity was found to be 1× 10^-4 S/cm2.Example 9:All the steps are similar to one in Embodiment 1, except that in this embodiment for the fibrillation process was for fabricating a separator for a Zn bat-10 tery:The procedure is similar to Embodiment 1 step 2, except that, in this embodiment, pre-zincified polyphenylene sulfide powder, cellulose fibre, and PTFE powder are mixed according to the weight percentage of 91%:3%:6%. The measured porosity was 6%. The pores were filled with 1M Zn(CF3SO3)2 elec-15 trolytes and the measured Zn ion conductivity was found to be 5*10-3 S/cm-1.A person skilled in the art will understand that the figures are just principal drawings. The relative proportions of individual elements may also be distorted.It should be noted that the above-mentioned embodiments illustrate rather 20 than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. Use of the verb “comprise”, and its conjugations does not exclude the presence of elements or steps other than 25 those stated in a claim. The article “a” or “an” preceding an element does not exclude the presence of a plurality of such elements.The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.30P31227NO00 description and claims
Claims
34950820C l a i m s1. Solid state separator for a battery, the solid state separator comprising:- a first layer including a pre-lithiated or pre-sodiated polyphenylene 5 sulfide (PPS) cellulose nanofibre (CelNF) composite free-standing film;- a second layer including a porous polyolefin film; and- a third layer including a ceramic nanolayer provided in-between the first and second layers.2. Solid state separator according to claim 1, wherein the second layer 10 includes polyethylene (PE) and/or polypropylene (PP).3. Solid state separator according to claim 1 or 2, wherein the thickness of the second layer is in the range 3-15 µm, preferably 5-10 µm.4. Solid state separator according to any one of the preceding claims, wherein the first layer includes PPS, CelNF, and polytetrafluoroethylene 15 (PTFE) powder with a weight ratio of 89-97%: 0.1-5%: 3-8%, preferably 90-94%: 1-3%: 4-6%, respectively.5. Solid state separator according to any one of the preceding claims, wherein the ceramic nanolayer has a thickness in the range 30-300 nm.6. Solid state separator according to any of the preceding claims, wherein 20 the first layer has a thickness of 5-45 μm, preferably10-30 μm, and even more preferably 15-25 μm.7. Solid state separator according to any one of the preceding claims, wherein the first layer has a porosity lower than 10%, preferably lower than 3%.25 8. Solid state separator according to any one of the preceding claims, wherein the third layer includes one or more of the following:- alumina,- a Li-rich ceramic, such as Li salts, Li rich cathode materials, lithium phosphorous Oxynitride (LiPON), or lithium titanate,34950821- a highly porous material, such as carbon nanospheres or metalorganic framework (MOF) materials.9. Solid state separator according to any one of the preceding claims, where in the separator has a thickness in a range of 10-60 μm, prefera-5 bly 15-30 μm, and even more preferably 20-25 μm.10.Solid state separator according to any one of the preceding claims, where in the solid state separator has a width in the range of 5 -160 cm.11.Solid state battery including a solid state separator according to any one 10 of the preceding claims.12.Solid state battery according to claim 11, wherein the solid state battery is a Li- or Na-ion battery.13.A method for producing a free-standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film, the 15 method including the steps of:- mixing and milling metal chloride dissolved in deionized water (DIW), tetrachloro-p-benzoquinone (TCBQ) and PPS powder to form a mixed slurry;- transferring the mixed slurry to a reactor for hydrothermal treatment; 20 - washing and filtering the hydrothermally treated mixture in a centrifuge;- drying the filtered solution to disintegrate PPS powder;- mixing the disintegrated PPS powder with cellulose fibres and polytetrafluoroethylene (PTFE) powder at a temperature at which the PTFE 25 powder is in a glass state to obtain a mixed solution;- griding the mixed solution in dry, compressed air;- compacting the grinded, mixed solution through one or more rollers to obtain a film; and- passing the film through a hot calendering machine to obtain the free-30 standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film.3495082214.A method for producing a free-standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film, the method including the steps of:- mixing and milling metal chloride dissolved in deionized water,5 tetrachloro-p-benzoquinone (TCBQ), PPS powder and cellulose fibres to form a mixed slurry;- transferring the mixed slurry to a reactor for hydrothermal treatment; - washing and filtering the hydrothermally treated mixture in a centrifuge;10 - drying the filtered solution to disintegrate PPS powder;- mixing the disintegrated PPS powder with polytetrafluoroethylene (PTFE) powder at a temperature at which the PTFE powder is in a glass state to obtain a mixed solution;- griding the mixed solution in dry, compressed air;15 - compacting the grinded, mixed solution through one or more rollers to obtain a film; and- passing the film through a hot calendering machine to obtain the freestanding, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film.20 15. The method according to claim 13 or 14, wherein the metal chloride is one or more of the following:- lithium chloride;- sodium chloride;- magnesium chloride;25 and aluminum chloride.16.The method according to any one of claims 13-15 wherein the PPS powder is a linear chain and end cross-linked semi-crystalline PPS powder, with a degree of crystallinity > 60% in the range 1-25 μm, preferably 1-5 µm.30 17.The method according to any one of claims 13-16, wherein the mass ratio of metal chloride, DIW and TCBQ to the total mass of PPS is1:30:5:100.3495082318.The method according to any one of claims 13-17, wherein the hydrothermal treatment is performed at a reaction temperature of approximately 210 °C, for two hours and a vapour pressure of 60-70 bar.19.The method according to any one of claims 13-18, wherein the mixing 5 of PPS powder with cellulose fibres and PTFE takes place at a temperature of 45-50°C.20.The method according to any one of claims 13-19, wherein the griding is performed in an air jet mill pre-heated by compressed air to a temperature of 40-50 °C.10 21.The method according to any one of claims 13-20, wherein the step of compacting the grinded, mixed solution through one or more rollers includes producing a film with a thickness of 1.0-3.0 mm, preferably 1.0-1.5 mm.22.The method according to any one of claims 13-21, wherein the method, 15 prior to passing the film through the hot calendering machine, includes the step of cold-rolling the film at a roller temperature of 40-70°C, preferably 45-55°C, to obtain a film with a thickness of 0.3-0.5 mm.23.The method according to any one of claims 13-22, wherein the hot calendering machine has a roller temperature of 120-140°C, preferably 20 1250-130°C.24.The method according to claim 23, wherein friction in rollers of the calendaring machine is controlled in a range of 1-20%, preferably 8-12%, while the line load is in a range of 500-250 N/mm, preferably 350-370 N/mm,25 25.Method of producing a solid state separator for a battery, the method including producing a free-standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film according to the method of any one of claims 12-24, the method further comprising the steps of:34950824- laminating a film of porous polyolefin to the PPS cellulose nanofibre film by means of a glue including a ceramic nanolayer.26.System for carrying out the method of claim 25, the system comprising:- primary storage tanks for metal chloride, deionized, water tetrachloro-5 p-benzoquinone (TCBQ), PPS powder and optionally cellulose fibre,- a mixer for mixing content from the primary storage tanks into a mixed slurry;- a reactor for hydrothermal treatment of the mixed slurry;- a centrifuge for washing and filtering the hydrothermally treated slur-10 ry;- means for drying the filtered solution to disintegrate PPS powder;-secondary storage tanks for disintegrated PPS powder, polytetrafluoroethylene (PTFE) powder and optionally cellulose nanofibres (if not part of the primary storage tanks);15 - a mixer for mixing content from the secondary storage tanks;- a grinder for grinding the mixed solution in compressed air;- one or more pairs of rollers for compacting the grinded solution into a film;- a hot calendaring machine through which the compacted film is passed 20 to obtain a free-standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film; and optionally - a laminator to add a film of porous polyolefin to the free-standing, pre-lithiated or pre-sodiated polyphenylene sulfide (PPS) cellulose nanofibre composite film by means of a ceramic nanolayer glue to obtain a 25 solid state separator.34950825P a t e n t k r a v1. Faststoffseparator for et batteri, faststoffseparatoren omfattende:- et første lag inkludert en frittstående komposittfilm av forhåndslitiert eller forhåndsnatriumisert polyfenylensulfid (PPS) og cellulosenanofiber (CelNF);5 - et andre lag inkludert en porøs polyolefinfilm; og- et tredje lag inkludert et keramisk nanolag tilveiebrakt mellom de første og andre lagene.2. Faststoffseparator ifølge krav 1, hvor det andre laget inkluderer polyetylen (PE) og/eller polypropylen (PP).10 3. Faststoffseparator ifølge krav 1 eller 2, hvor tykkelsen av det andre laget er i området 3–15 μm, fortrinnsvis 5–10 μm.4. Faststoffseparator ifølge et hvilket som helst av de foregående kravene, hvor det første laget inkluderer PPS, CelNF og polytetrafluoretylen (PTFE)-pulver med et vektforhold på henholdsvis 89–97 %: 0,1–5 %: 3–8 %, fortrinnsvis 90–94 %: 1–3 %: 4–6 %.15 5. Faststoffseparator ifølge et hvilket som helst av de foregående kravene, hvor det keramiske nanolaget har en tykkelse i området 30–300 nm.6. Faststoffseparator ifølge et hvilket som helst av de foregående kravene, hvor det første laget har en tykkelse på 5–45 μm, fortrinnsvis 10–30 μm og mer fortrinnsvis 15–25 μm.7. Faststoffseparator ifølge et hvilket som helst av de foregående kravene, hvor det første 20 laget har en porøsitet lavere enn 10 %, fortrinnsvis lavere enn 3 %.8. Faststoffseparator ifølge et hvilket som helst av de foregående kravene, hvor det tredje laget inkluderer én eller flere av følgende:- alumina,- en Li-rik keramikk, slik som Li-salter, Li-rike katodematerialer, litium-fosfor-oksynitrid 25 (LiPON), eller litiumtitanat,- et høyporøst materiale, slik som karbonnanosfærer eller metallorganisk rammeverk (MOF)-materialer.9. Faststoffseparator ifølge et hvilket som helst av de foregående kravene, hvor separatoren har en tykkelse i et område på 10–60 μm, fortrinnsvis 15–30 μm og mer fortrinnsvis 20– 30 25 μm.10. Faststoffseparator ifølge et hvilket som helst av de foregående kravene, hvor faststoffseparatoren har en bredde i området 5–160 cm.3495082611. Faststoffbatteri inkludert en faststoffseparator ifølge et hvilket som helst av de foregående kravene.12. Faststoffbatteri ifølge krav 11, hvor faststoffbatteriet er et Li- eller Na-ionbatteri.13. Fremgangsmåte for å fremstille en frittstående komposittfilm av forhåndslitiert eller for-5 håndsnatriumisert polyfenylensulfid (PPS) og cellulosenanofiber, fremgangsmåten inkluderende trinnene:- å blande og male metallklorid oppløst i avionisert vann (DIW), tetraklor-p-benzoquinon (TCBQ) og PPS-pulver for å tildanne en blandet slurry;- å overføre den blandende slurryen til en reaktor for hydrotermisk behandling;10 - å vaske og filtrere den hydrotermisk behandlede blandingen i en sentrifuge;- å tørke den filtrerte løsningen for å desintegrere PPS-pulver;- å blande det desintegrerte PPS-pulveret med cellulosefibre og polytetrafluoretylen (PTFE)-pulver ved en temperatur ved hvilken PTFE-pulveret er i glasstilstand, for å oppnå en blandet løsning;15 - å male den blandede løsningen i tørr trykkluft;- å komprimere den malte, blandede løsningen gjennom én eller flere valser for å oppnå en film; og- å sende filmen gjennom en varmkalandreringsmaskin for å oppnå den frittstående komposittfilmen av forhåndslitiert eller forhåndsnatriumisert polyfenylensulfid (PPS) og cellu-20 losenanofiber.14. Fremgangsmåte for å fremstille en frittstående komposittfilm av forhåndslitiert eller forhåndsnatriumisert polyfenylensulfid (PPS) og cellulosenanofiber, fremgangsmåten inkluderende trinnene:- å blande og male metallklorid oppløst i avionisert vann, tetraklor-p-benzoquinon 25 (TCBQ), PPS-pulver og cellulosefibre for å tildanne en blandet slurry;- å overføre den blandende slurryen til en reaktor for hydrotermisk behandling;- å vaske og filtrere den hydrotermisk behandlede blandingen i en sentrifuge;- å tørke den filtrerte løsningen for å desintegrere PPS-pulver;- å blande det desintegrerte PPS-pulveret med polytetrafluoretylen (PTFE)-pulver ved en 30 temperatur ved hvilken PTFE-pulveret er i glasstilstand, for å oppnå en blandet løsning;- å male den blandede løsningen i tørr trykkluft;- å komprimere den malte, blandede løsningen gjennom én eller flere valser for å oppnå en film; og- å sende filmen gjennom en varmkalandreringsmaskin for å oppnå den frittstående kom-35 posittfilmen av forhåndslitiert eller forhåndsnatriumisert polyfenylensulfid (PPS) og cellulosenanofiber.3495082715. Fremgangsmåte ifølge krav 13 eller 14, hvor metallkloridet er én eller flere av følgende:- litiumklorid;- natriumklorid;- magnesiumklorid;5 og aluminiumklorid.16. Fremgangsmåte ifølge et hvilket som helst av kravene 13–15, hvor PPS-pulveret er et lineærkjedet og endekryssbundet semikrystallinsk PPS-pulver, med en krystallinitetsgrad > 60 % i området 1–25 μm, fortrinnsvis 1–5 μm.17. Fremgangsmåte ifølge et hvilket som helst av kravene 13–16, hvor masseforholdet av 10 metallklorid, DIW og TCBQ mot den totale massen av PPS er 1:30:5:100.18. Fremgangsmåte ifølge et hvilket som helst av kravene 13–17, hvor den hydrotermiske behandlingen utføres ved en reaksjonstemperatur på omtrent 210 °C i to timer og ved et damptrykk på 60–70 bar.19. Fremgangsmåte ifølge et hvilket som helst av kravene 13–18, hvor blandingen av PPS-15 pulver med cellulosefibre og PTFE finner sted ved en temperatur på 45–50 °C.20. Fremgangsmåte ifølge et hvilket som helst av kravene 13–19, hvor malingen utføres i en luftstrålemølle forvarmet av trykkluft til en temperatur på 40–50 °C.21. Fremgangsmåte ifølge et hvilket som helst av kravene 13–20, hvor trinnet for å komprimere den malte, blandede løsningen gjennom én eller flere valser inkluderer å fremstille 20 en film med en tykkelse på 1,0–3,0 mm, fortrinnsvis 1,0–1,5 mm.22. Fremgangsmåte ifølge et hvilket som helst av kravene 13–21, hvor fremgangsmåten, før filmen sendes gjennom varmkalandreringsmaskinen, inkluderer trinnet å kaldvalse filmen ved en valsetemperatur på 40–70 °C, fortrinnsvis 45–55 °C, for å oppnå en film med en tykkelse på 0,3–0,5 mm.25 23. Fremgangsmåte ifølge et hvilket som helst av kravene 13–22, hvor varmkalandreringsmaskinen har en valsetemperatur på 120–140 °C, fortrinnsvis 125–130 °C.24. Fremgangsmåte ifølge krav 23, hvor friksjon i valsene i kalandreringsmaskinen kontrolleres i et område på 1–20 %, fortrinnsvis 8–12 %, mens linjebelastningen er i et område på 500–250 N/mm, fortrinnsvis 350–370 N/mm.30 25. Fremgangsmåte for å fremstille en faststoffseparator for et batteri, fremgangsmåten inkluderende å fremstille en frittstående komposittfilm av forhåndslitiert eller forhåndsnatriumisert polyfenylensulfid (PPS) og cellulosenanofiber ifølge fremgangsmåten ifølge et hvilket som helst av kravene 12–24, fremgangsmåten videre omfattende trinnene:34950828- å laminere en film av porøs polyolefin til PPS-cellulosenanofiber-filmen ved hjelp av et lim inkludert et keramisk nanolag.26. System for utførelse av fremgangsmåten ifølge krav 25, systemet omfattende:- primære lagringstanker for metallklorid, avionisert vann, tetraklor-p-benzoquinon 5 (TCBQ), PPS-pulver og valgfritt cellulosefibre,- en blandeanordning for å blande innhold fra de primære lagringstankene til en blandet slurry;- en reaktor for hydrotermisk behandling av den blandede slurryen;- en sentrifuge for å vaske og filtrere den hydrotermisk behandlede slurryen;10 - midler for å tørke den filtrerte løsningen for å desintegrere PPS-pulver;- sekundære lagringstanker for desintegrert PPS-pulver, polytetrafluoretylen (PTFE)-pulver og valgfritt cellulosenanofibre (hvis ikke det er del av de primære lagringstankene); - en blandeanordning for å blande innhold fra de sekundære lagringstankene;- en mølle for å male den blandende løsningen i trykkluft;15 - ett eller flere par med valser for å komprimere den malte løsningen til en film;- en varmkalandreringsmaskin gjennom hvilken den komprimerte filmen sendes for å oppnå en frittstående komposittfilm av forhåndslitiert eller forhåndsnatriumisert polyfenylensulfid (PPS) og cellulosenanofiber; og valgfritt- en laminator for å påføre en film av porøs polyolefin på den frittstående komposittfilmen 20 av forhåndslitiert eller forhåndsnatriumisert polyfenylensulfid (PPS) og cellulosenanofiber ved hjelp av et lim av keramisk nanolag for å oppnå en faststoffseparator.
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IPC classesH01M 50/417H01M 50/434H01M 50/44H01M 50/457CPC classesH01M 50/417H01M 50/434H01M 50/44H01M 50/457

Citations

CN 108878751 B (B)US 2019237731 A1 (A1)US 2016204406 A1 (A1)US 2023387548 A1 (A1)US 2018043656 A1 (A1)

Applicants, owners and inventors

Owners
ZNL ENERGY AS
Kokstadvegen 23 5257 KOKSTAD NO (BERGEN Municipality, Vestland county)Org. number: 928467597Inventors
Jan Børge Sagmo
Hopsåsen 50 5221 NESTTUN NO (BERGEN Municipality, Vestland county)
Benjamin Ferstad
Magnus Vigrestads vei 4 4023 STAVANGER NO (STAVANGER Municipality, Rogaland county)
Syed Talat Ali
Ola Frosts veg 2A, 1204 7031 TRONDHEIM NO (TRONDHEIM Municipality, Trøndelag county)
De Chen
Stokkbekken 6 7048 TRONDHEIM NO (TRONDHEIM Municipality, Trøndelag county)

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HÅMSØ PATENTBYRÅ AS
HÅMSØ PATENTBYRÅ AS

Org. number: 918752900

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Reference: P31227NO00

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