TW406448B - Secondary battery separator and process for making same - Google Patents

Abstract

A secondary battery separator comprises a fibrous core coated with a polymer having improved electrode adhesion properties in unitary laminated construction. Vacuum removal of plasticizer without solvent extraction prevents brittleness and results in microporosity in a thin layer of enhanced ion conductivity.

Description

Excuse me, please expressly clarify * ^^ year ^ Japan, the Central Standards Bureau of the Ministry of Economic Affairs, whether there is any change in the content of the printed copy of the repair price * < Scope of the invention > Especially a battery separator plate element having improved functions and manufacturing methods. < Background of the invention > In the construction of any type of battery, there must be six types of elements, namely, a positive electrode and a negative electrode 'a case', a separator, an electrolytic substance, and a current collecting plate. The separator is an important component because it must be able to move ions through it during charging and discharging without allowing electrons to directly flow between the electrodes, forming a short-circuit current that prevents electrons from flowing from the positive electrode to the negative electrode through the circuit. Rechargeable lithium iron batteries are composed of extremely thin layers of components. The distance between the electrodes should be as short as possible. It is important to improve the efficiency of ion movement, but it must not be shortened to allow electrons to flow. The separator is made of an extremely thin plastic plate, and is made porous by removing the plasticizer by a molding film. Generally, lithium salts are taboo because they tend to react with the electrode in an aqueous solution, so they are maintained in a non-aqueous environment. Organic solvents such as propylene carbonate or ethylene carbonate are commonly used where the lithium salt dissolve is truly dispersible. Other solvents are tetrahydrofuran, 1, 2, 2-dimethoxyethane, dimethyl carbonate, and diethoxyethane. For a discussion of traditional solvents on lithium-solubles, please refer to S. Hassain, "Rechargeable Lithium Batteries" (Ambient Temperature), Book Title "Batteries and Fuel Cells", edited by D. Linden, Second edition, 1995, published by McGraw-Hill Books. Of course, the plastic divider must be stable to the chosen solvent. In US Patent Nos. 4,138,459, 3,801,404 and 3,843,761, it is disclosed that the crystalline polyolefin is extended by 3 g below the transition temperature; using the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ) " '(Please read the notes on the back before filling out this page).

Excuse me, please expressly clarify * ^^ year ^ Japan, the Central Standards Bureau of the Ministry of Economic Affairs, whether there is any change in the content of the printed copy of the repair price * < Scope of the invention > The present invention relates to rechargeable solid-state lithium iron batteries, Especially a battery separator plate element having improved functions and manufacturing methods. < Background of the invention > In the construction of any type of battery, there must be six types of elements, namely, a positive electrode and a negative electrode 'a case', a separator, an electrolytic substance, and a current collecting plate. The separator is an important component because it must be able to move ions through it during charging and discharging without allowing electrons to directly flow between the electrodes, forming a short-circuit current that prevents electrons from flowing from the positive electrode to the negative electrode through the circuit. Rechargeable lithium iron batteries are composed of extremely thin layers of components. The distance between the electrodes should be as short as possible. It is important to improve the efficiency of ion movement, but it must not be shortened to allow electrons to flow. The separator is made of an extremely thin plastic plate, and is made porous by removing the plasticizer by a molding film. Generally, lithium salts are taboo because they tend to react with the electrode in an aqueous solution, so they are maintained in a non-aqueous environment. Organic solvents such as propylene carbonate or ethylene carbonate are commonly used where the lithium salt dissolve is truly dispersible. Other solvents are tetrahydrofuran, 1, 2, 2-dimethoxyethane, dimethyl carbonate, and diethoxyethane. For a discussion of traditional solvents on lithium-solubles, please refer to S. Hassain, "Rechargeable Lithium Batteries" (Ambient Temperature), Book Title "Batteries and Fuel Cells", edited by D. Linden, Second edition, 1995, published by McGraw-Hill Books. Of course, the plastic divider must be stable to the chosen solvent. In US Patent Nos. 4,138,459, 3,801,404 and 3,843,761, it is disclosed that the crystalline polyolefin is extended by 3 g below the transition temperature; using the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ) " '(Please read the notes on the back before filling this page). Install. -β year 406446 A7 B7

Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention () Hydrocarbon membrane to produce a porous plastic separator. However, this elongated polymer is harmful because the distance between the electrodes is too large due to the negligible control of the uniform pore size. US Patent 4,994,335 discloses a method of elongation, in which the strain rate and temperature are tightly controlled to produce microporosity in only one direction, so that adjacent unstretched flat plane parts are connected in a two-dimensional direction to become delicate. Fibrosis. A serious problem arises when the electrolytic lithium salt reacts in the completed battery to form lithium dendritic crystals, which tends to fill the empty space of the separator plate to generate a conductive path, causing the battery to short circuit. . A method for preventing a short circuit caused by dendritic crystals is disclosed in US Patent No. 5,427,872, by using a polypropylene or polyethylene synthetic partition plate which is inert to dendritic crystal reactions together with, for example, polyvinyl fluoride Intervening fluorinated polymer, the porosity can be maintained by preventing the penetration of dendritic crystals by the second separator for electrode protection. In another option, U.S. Patent Nos. 5,460,904, 5,296,318, 5,429,891 disclose separators including a self-supporting membrane formed from a copolymer of polyvinylidene fluoride (PVdF) and hexafluoropropylene (HFP). Before casting, the copolymer is mixed with a medium and heated to a high temperature to boil a plasticizer solvent such as dibutyl phthalate (DBP) and a filler such as Si02. After casting, the plasticizer is extracted together with a solvent such as diethyl ether and the like, and is replaced by a battery electrolyte. The space occupied by the plasticizer is filled by the electrolyte, and becomes a network that can diffuse the ion space. In a preferred embodiment, the > dry separator can be coupled to a pressurized electrode by heating before the electrolyte is loaded. 4 (Please read the notes on the back before filling this page)

L-* D This paper size applies to China National Standard (CNS) A4 (210X297 mm) 406446 A7 B7

Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention () Hydrocarbon membrane to produce a porous plastic separator. However, this elongated polymer is harmful because the distance between the electrodes is too large due to the negligible control of the uniform pore size. US Patent 4,994,335 discloses a method of elongation, in which the strain rate and temperature are tightly controlled to produce microporosity in only one direction, so that adjacent unstretched flat plane parts are connected in a two-dimensional direction to become delicate. Fibrosis. A serious problem arises when the electrolytic lithium salt reacts in the completed battery to form lithium dendritic crystals, which tends to fill the empty space of the separator plate to generate a conductive path, causing the battery to short circuit. . A method for preventing a short circuit caused by dendritic crystals is disclosed in US Patent No. 5,427,872, by using a polypropylene or polyethylene synthetic partition plate which is inert to dendritic crystal reactions together with, for example, polyvinyl fluoride Intervening fluorinated polymer, the porosity can be maintained by preventing the penetration of dendritic crystals by the second separator for electrode protection. In another option, U.S. Patent Nos. 5,460,904, 5,296,318, 5,429,891 disclose separators including a self-supporting membrane formed from a copolymer of polyvinylidene fluoride (PVdF) and hexafluoropropylene (HFP). Before casting, the copolymer is mixed with a medium and heated to a high temperature to boil a plasticizer solvent such as dibutyl phthalate (DBP) and a filler such as Si02. After casting, the plasticizer is extracted together with a solvent such as diethyl ether and the like, and is replaced by a battery electrolyte. The space occupied by the plasticizer is filled by the electrolyte, and becomes a network that can diffuse the ion space. In a preferred embodiment, the > dry separator can be coupled to a pressurized electrode by heating before the electrolyte is loaded. 4 (Please read the notes on the back before filling this page)

L-* D This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 06446 A7 B7

V. Description of the invention () The polymer fiber printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives is made into polymer fibers, and finally converted into fibers with a diameter of about 0.1 micron and a length of about 1.5 micron. Structurally, the fibers of the base block are randomly arranged to form small holes throughout the base block. These base blocks are manufactured by stacking fibers on a moving transmission track to a desired thickness, and pressing them into a sheet by a roller in the same way as paper. In addition, the fiber pieces may be melted and broken up. The final size of the fiber-based block is preferably 0 to 75 to 5.0 mil thick, and the density is between 15 to 50 g / m3. The copolymer of the separator fiber is selected from polyethylene, polypropylene, or a polyvinyl alcohol, and is produced by a conventional method. The fibers are made from high-molecular polymers in a semi-free twisted manner. A combination of copolymers can theoretically be used. The copolymer has been formed into a sheet-like product, and its price is very low. It is manufactured according to specifications and has good reworkability in battery applications. The strength and elasticity of a fibrous base can be attributed to its resistance to rupture. The good adhesion of the layer is obtained by properly controlling the fibrous base block of the second polymer coated on the separator. The choice of coating polymer depends greatly on the base material used. When polyethylene or polypropylene is used, polyvinylidene fluoride is preferably used as the copolymer coating material. For polyvinyl alcohol pellets, it is better to use a water-compatible coating such as Kynar Latex (Eif-xuan todieTTi) or polytetrafluoroethylene that is dispersible such as Dupont T-30. The basic requirements are The coating should be porous or have the ability to become porous to allow the transport of ions. Typically, powdery copolymers can be dispersed in organic solvents such as propylene copper. The mixture is used in a fibrous state after adding a plasticizer. Heart block. A polymer film is left after the acetone carrier is evaporated. Then it is heated in a vacuum to remove the plasticizer. It can be added at a temperature of 55 to 160 ° C without damaging the separator. This paper size applies to Chinese national standards (CNS) A4 specification (210 X 2M mm) (Please read the notes on the back before filling out this page) Equipment · Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 406446 V. Restriction Instructions () US Patent Ν 〇 4,550,064 revealed that the separator includes two layers. The first inner layer is made of microporous polyethylene (Celgard brand name) or glass fiber, and its surface is more hydrophilic due to the coating of imidazole. These separators together with Positive electrode use The positive electrode is made with an elastomer adhesive of propylene or ethylene. The separator used in the past has some disadvantages. The multilayer separator has a stepped porosity gradient, so that the electrolyte in each layer has Different diffusion constants. The transfer of ions may be hindered, which may interfere with the discharge rate of the battery, but may also affect its capacity. When the separator is made of PVdF or HFP, the leaching of the solvent causes the brittleness to cause the substantial formation process Lack of production level. The combination of leaching solvent and plasticizer but cannot be reused, which also causes disposal problems. ≪ General of the invention > According to the present invention, it is suitable for a separator plate system for lithium batteries. It is made of a preformed non-woven porous mat, which includes a first copolymer of polypropylene, polyethylene, or polyvinyl alcohol, and is coated with a second copolymer. The coating layer of the porous copolymer is most Fortunately, polyvinylidene fluoride (PVDF) can be obtained by mixing the first copolymer with a low boiling point solvent. The solvent can be selected from one or more non-aromatic fatty diesters to form polymers and diesters. The mixture is laminated. The resulting separator, which can be placed between the anode and the cathode, includes a porous layered central substrate, the layers of which have opposite surfaces, and at least one surface is coated with a copolymer coating. The plasticizer that removes the solvent by air. The separator has sufficient permeability to allow the ions in the electrolyte to pass through, and the carbon-containing or other lithium inserts are used as the anode, and the lithium metal oxide is used as the cathode. This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page), ΤΓ 406448 A7 B7

Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. 5. Description of the invention () Jets that are rolled or fully penetrated, and those that start from the rough side are most practical. When coating, the composition ratio of the mixed coating will affect the porosity and adhesion of the coating structure. The ratio of copolymerization to plasticizer is preferably about 2: 1 to 1:10, and the ratio of copolymer or plasticizer to acetone can be between about 1: 5 to 2: 1, which is often The 2C discharge curve (see example) shows the best results for a battery that can discharge 30% of its capacity. The ratio is expressed in w / w. Fillers such as Ti02 or Si02 are not necessary in providing material strength during coating. The battery parts that can be used together with the separator of the present invention are traditional electrodes, electrolytes, and current collection plate systems. Plastic electrodes and separators are well known in the field of solid (dry) lithium ion battery technology. In electrolytic solutions, typical lithium salts include LiPF6, LiBF4, LiC104, and UN (CF3S02). The best is Li [N (S02C2F5) 2]. Typical solution systems for the dispersion of lithium metal ions include diethyl and dimethyl carbonate or mixtures thereof, tetrahydrofuran, 1,2-dimethoxyethane, and other organic solvents that ionize lithium metal salts Wait. Generally speaking, a solvent with a low viscosity is preferred (its range is less than 0.5 at 25 ° C). In order to make the movement of ions easier, the absorption characteristics of water are important. This is because of lithium salts. The cloth exhibits a high degree of instability in an aqueous environment, and a suitable solvent must have a moisture content of less than 10 ppm. The electrodes of solid-state lithium-ion batteries are made of lithium compounds dispersed in a thin layer of porous plastic sheet. Any electrochemically compatible cathode and anode can be used as the battery separator of the present invention. In a typical solid-state lithium-ion battery, the cathode is a dispersed lithium salt with or without a binder. For example, LiMO, its 10 (Please read the precautions on the back before filling this page). Binding. Order-4. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 406446 5. Hair handle description () The secondary battery can discharge at least 3G% of its capacity when discharged at 2C. In use, the separator is a composition of a rechargeable lithium battery. The battery includes a case, preferably sealed with plastic, and two electrodes in the case, including anodes containing carbon or other lithium inserts. Anode components include amorphous graphite, coke, filamentous carbon, or various combinations thereof, and cathodes of lithium metal oxides, and electrolyte solutions in the shell, which contain a lithium metal salt that can be ionized in an organic solvent, and the salt can be dispersed. In an organic solvent, a current collecting plate is electrically connected to each pole, and a separator plate is interposed between the two poles. The separator plate includes a fibrous core block having a surface, and a porous copolymer coating is applied. Take a heart block on at least one surface. Printed by the Central Labor Department of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (please read the note on the back, and then fill out this page) Γ During the manufacturing process of the partition plate, its fibrous polymer core block is A mixture of the second polymer of the aromatic plasticizing solvent and acetone is applied, and then heated under a vacuum to remove the plasticizer to produce a microporous layer having conductivity to lithium salt ions. A rechargeable battery with a simple and single structure is produced by orderly arranging a carbon-containing or other lithium-intercalated anode, a lithium metal oxide cathode, and a separator plate in a pile. Carbon or other lithium intercalated anode and cathode covered with lithium salt polymer, and the anode, cathode and separator are layered by heat and pressure treatment to make the anode, cathode and separator fully adhered into one body structure. In a further battery embodiment, another cathode is added to the layered lithium ion battery. The method is to arrange a second partition plate on the outer side of the anode, and arrange them in order to form a pile sandwiched between the anode and a second cathode, which becomes a double structure. s-s +, where + represents a cathode layer and one represents an anode layer, and S is a separator. Separator thickness This paper size applies the Chinese standard (CMS > A4 size (210X297mm > A7 B7

406448 V. Description of the invention () M and 0 are Co, Ni, Mn or V metal compounds with appropriate valence. Conventional manufacturing methods of cathodes suitable for use with the separator are disclosed in U.S. Patent Nos. 5,296,318, 4,550,064, 5,260,148, 5,518,842, and 5,380,606, etc., for reference. The anode of a solid-state lithium-ion battery is typically a carbonaceous material, including various forms of painted graphite or painted coke. Lithium ions are often incorporated into carbonaceous materials to produce LiC6 stoichiometrically. U.S. Patent No. 5,219,680 discloses a method of making such an electrode by capturing amorphous carbon in a pre-mixed polymer, which is then polymerized by surrounding a metal collection element. U.S. Patent 5,514,490 discloses an unusual anode using a layered titanium sulfide with lithium interposed therebetween. Further forms that can be used for this separator include low density amorphous carbon and Raman spectrum as disclosed in U.S. Patent No. 5,401,598. A preferred carbonaceous or other lithium intercalation anode material is a compacted fibrous ink dispersed in a porous copolymer matrix. The patent of its forging method can be used for reference in this case. Other cathode and anode materials are described in Hassain, Supra. .. The collecting plate element that can be used in the battery of this case is traditional metal, and the collecting plate is better; the collecting plate is typical with most small punches. The liquid plastic electrode with dispersed active material is distributed or sprayed on the surface of the collecting plate. When the polymer penetrates the punching holes to contain the polymer on both sides, the strength can be increased, and when the type of multiple batteries is Each metal sheet collecting plate can give two current collecting surfaces. FIG. 1 shows a battery and a partition plate according to the present invention. One battery 11 paper paper size standard China National Standard (CNS) 8 4 specifications (210X297 mm) —- 1 ~ III '~ nn ^]. 1τΊ' II-(Please read the precautions on the back before filling in this Page) ~ Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs_ ^ 06448 B7_ V. Description of Seeding () Adjusted to balance the characteristic discharge capacity of the anode and cathode. < Brief description of the diagram > Fig. 1 shows a cross-sectional structure diagram of a typical plastic-layer battery. Figures 2a to 2d show the relationship between the various battery charging and discharging parameters and are plotted at right angles. Fig. 3 is a graph created according to Fig. 2, each point of which is derived from the data in Fig. 2. < Detailed description of the preferred embodiment > Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back before filling this page) In a solid-state rechargeable lithium-ion battery, The separator is particularly important, not only in the proper functioning of the battery, but also in its manufacturability. For the production technology of the anode, cathode and separator, there are many known manufacturing strategies' for people to evaluate, so that the ions can freely flow back and forth between the electrodes during continuous charging and discharging cycles. For example, the plies can be arranged and wound into tight circles' or they can be compressed by mechanical force. Ideally, a rugged layer with a highly elastic structure can accommodate a wider range of applications, while providing great permeability in a case containing battery parts. Since separators tend to short-circuit the cells during stacking due to cracks during layering, the conventional layering technology has left considerable experimental interest. Rupture is defined as a break or compression of the partition. If such a battery is layered under reduced pressure in order to avoid cracking, it is often pulled away or the interlayer interface becomes discontinuous, which greatly reduces the efficiency of the battery. The partition plate of the present invention includes two parts, an inner central base block made of a fibrous copolymer, and an outer coating made of a second copolymer. The central base is a fibrous composition, which is made in rollers pre-formed by manufacturers such as Web Dynamics and Hollingsworth / ^^. These materials are made of small paper. The paper size is applicable to Chinese National Standards (CNS) Eight Regulations # (210X297 public copy) 406448 A7 B7

X Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () The manufacturing method of the separator according to the present invention is as follows: A non-woven polyethylene fiber-like substrate (Web Dynamix, Px0074) is purchased from the market. Its material manufacturing specifications include a thickness of 2.5 mil and a diameter of no more than 0.1 leg. Its products have a rough surface and another smooth surface. The density of the material is determined empirically as 28 g / m3. The manufacturer of these fiber sheets is STET, which is coated with complete rolls. The copolymer is coated by applying a coating of approximately 12 feet in length (a roll having a diameter of 12 inches) from the entire fiber sheet. The mixed coating contains 15g of Kynar brand 741 polyvinylidene fluoride copolymer, 30g of diethylsuccinate (as a plasticizer) 'and 150ml of reagent grade acetone. The mixture is heated to 70 ° in a closed container. C is used to melt the ingredients, and then cooled to room temperature. A section of the whole fiber sheet is placed on flat glass with its smooth—edge facing glass. Excess mixed paint (approximately 75ml) was poured out of the fiber sheet and evenly distributed on the surface by a roller. After air-drying, the fiber sheet was turned over and the coating solution was applied to the smooth surface. The coating weight is 100g. The base thickness is 2.5mil, and the coating thickness is about 3.0mil. Combination of separator and solid-state lithium battery produced by this method: The cathode includes 65% of LiMn204 (Chemetal) dispersed in the substrate, and its composition is almost the same as the copolymer coating of the separator. Plastic electrodes also contain 5.4% (Super-P brand) to improve conductivity. Both sides of the cathode sheet are laminated with a bulging metal-aluminum collecting plate element. The battery is assembled in a dual mode, which is arranged by the following rigorous sequence: a cathode element, a separator plate, an anode element, a second separator plate, and a second cathode element. Each component is rolled and melted into layers by a roller at full pressure. 13 The paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) " '~~~ * (Please read the precautions on the back before filling this page) -Packed * 11 line '06446 A7 B7

V. Description of the invention () The polymer fiber printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives is made into polymer fibers, and finally converted into fibers with a diameter of about 0.1 micron and a length of about 1.5 micron. Structurally, the fibers of the base block are randomly arranged to form small holes throughout the base block. These base blocks are manufactured by stacking fibers on a moving transmission track to a desired thickness, and pressing them into a sheet by a roller in the same way as paper. In addition, the fiber pieces may be melted and broken up. The final size of the fiber-based block is preferably 0 to 75 to 5.0 mil thick, and the density is between 15 to 50 g / m3. The copolymer of the separator fiber is selected from polyethylene, polypropylene, or a polyvinyl alcohol, and is produced by a conventional method. The fibers are made from high-molecular polymers in a semi-free twisted manner. A combination of copolymers can theoretically be used. The copolymer has been formed into a sheet-like product, and its price is very low. It is manufactured according to specifications and has good reworkability in battery applications. The strength and elasticity of a fibrous base can be attributed to its resistance to rupture. The good adhesion of the layer is obtained by properly controlling the fibrous base block of the second polymer coated on the separator. The choice of coating polymer depends greatly on the base material used. When polyethylene or polypropylene is used, polyvinylidene fluoride is preferably used as the copolymer coating material. For polyvinyl alcohol pellets, it is better to use a water-compatible coating such as Kynar Latex (Eif-xuan todieTTi) or polytetrafluoroethylene that is dispersible such as Dupont T-30. The basic requirements are The coating should be porous or have the ability to become porous to allow the transport of ions. Typically, powdery copolymers can be dispersed in organic solvents such as propylene copper. The mixture is used in a fibrous state after adding a plasticizer. Heart block. A polymer film is left after the acetone carrier is evaporated. Then it is heated in a vacuum to remove the plasticizer. It can be added at a temperature of 55 to 160 ° C without damaging the separator. This paper size applies to Chinese national standards (CNS) A4 size (210 X 2M mm) (Please read the precautions on the back before filling out this page) Equipment · 406446 A7 B7 V. Hair handle description () The plasticizer of the present invention is non-aromatic, aliphatic Its general molecular formula is R100C (CH2) nC00R2, where Ri and R2 are methyl, ethyl, propyl, butyl, or a combination thereof, and η is from 1 to about 7. Generally speaking, the preferred plasticizer It has a low boiling point (less than 75 ° C under reduced pressure). It can be effectively removed under heat. The formation of the present invention has three advantages over traditional methods. First, the solvent extraction step can be eliminated. Second, the plasticizer can be recovered and reused. Third, the solvent extraction step The omission can avoid the “dry-out” of the solvent, which can make the finished separator hard or brittle. In addition to volatile and useful plasticizing characteristics, the plasticizer must be able to be uniformly and finely dispersed on the coating. After removing the microporous network structure, the remaining coating can allow ions to pass through. Alternatively, the lithium salt contained in the electrolyte solution can be included in the copolymer, plasticizer, and acetone mixture to remove the copolymerization. After the plasticizer in the coating, uniformly dispersed lithium salt can be obtained immediately before the layer is formed. Many polymer substrates are commercially available and are manufactured in a way that the rough side and the smooth side are opposite. It is important The thing is that when coating the polymer, it should be done from the rough side first, and then change the side to coat the smooth side. If the order of execution is reversed, the coating will not adhere properly and fall off from the center block. The applicant and others believe that It is not necessary to cling to any particular theory. Of course, the second polymer is easier to adhere to the rough surface. The copolymer mainly passes through the center block to reach a smooth surface. Here, a compatible interface and an adhesive surface are formed. Facilitates the application of paint on the opposite surface. Traditional methods of ZHUHE can be used for coating work, including spraying or slicing, casting, or rolling under control. In engineering practice, continuous 9 paper sizes Applicable to Chinese National Standards (CNS > Α4 specification (210 × 297 mm) (Please read the note on the back ^^ before filling out this page), · Γ · ί · Printed by the Shellfish Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs «. 406448 A7 B7

Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. 5. Description of the invention () Jets that are rolled or fully penetrated, and those that start from the rough side are most practical. When coating, the composition ratio of the mixed coating will affect the porosity and adhesion of the coating structure. The ratio of copolymerization to plasticizer is preferably about 2: 1 to 1:10, and the ratio of copolymer or plasticizer to acetone can be between about 1: 5 to 2: 1, which is often The 2C discharge curve (see example) shows the best results for a battery that can discharge 30% of its capacity. The ratio is expressed in w / w. Fillers such as Ti02 or Si02 are not necessary in providing material strength during coating. The battery parts that can be used together with the separator of the present invention are traditional electrodes, electrolytes, and current collection plate systems. Plastic electrodes and separators are well known in the field of solid (dry) lithium ion battery technology. In electrolytic solutions, typical lithium salts include LiPF6, LiBF4, LiC104, and UN (CF3S02). The best is Li [N (S02C2F5) 2]. Typical solution systems for the dispersion of lithium metal ions include diethyl and dimethyl carbonate or mixtures thereof, tetrahydrofuran, 1,2-dimethoxyethane, and other organic solvents that ionize lithium metal salts Wait. Generally speaking, a solvent with a low viscosity is preferred (its range is less than 0.5 at 25 ° C). In order to make the movement of ions easier, the absorption characteristics of water are important. This is because of lithium salts. The cloth exhibits a high degree of instability in an aqueous environment, and a suitable solvent must have a moisture content of less than 10 ppm. The electrodes of solid-state lithium-ion batteries are made of lithium compounds dispersed in a thin layer of porous plastic sheet. Any electrochemically compatible cathode and anode can be used as the battery separator of the present invention. In a typical solid-state lithium-ion battery, the cathode is a dispersed lithium salt with or without a binder. For example, LiMO, its 10 (Please read the notes on the back before filling this page). Binding. Order -4. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7

406448 V. Description of the invention () M and 0 are Co, Ni, Mn or V metal compounds with appropriate valence. Conventional manufacturing methods of cathodes suitable for use with the separator are disclosed in U.S. Patent Nos. 5,296,318, 4,550,064, 5,260,148, 5,518,842, and 5,380,606, etc., for reference. The anode of a solid-state lithium-ion battery is typically a carbonaceous material, including various forms of painted graphite or painted coke. Lithium ions are often incorporated into carbonaceous materials to produce LiC6 stoichiometrically. U.S. Patent No. 5,219,680 discloses a method of making such an electrode by capturing amorphous carbon in a pre-mixed polymer, which is then polymerized by surrounding a metal collection element. U.S. Patent 5,514,490 discloses an unusual anode using a layered titanium sulfide with lithium interposed therebetween. Further forms that can be used for this separator include low density amorphous carbon and Raman spectrum as disclosed in U.S. Patent No. 5,401,598. A preferred carbonaceous or other lithium intercalation anode material is a compacted fibrous ink dispersed in a porous copolymer matrix. The patent of its forging method can be used for reference in this case. Other cathode and anode materials are described in Hassain, Supra. .. The collecting plate element that can be used in the battery of this case is traditional metal, and the collecting plate is better; the collecting plate is typical with most small punches. The liquid plastic electrode with dispersed active material is distributed or sprayed on the surface of the collecting plate. When the polymer penetrates the punching holes to contain the polymer on both sides, the strength can be increased, and when the type of multiple batteries is Each metal sheet collecting plate can give two current collecting surfaces. FIG. 1 shows a battery and a partition plate according to the present invention. One battery 11 paper paper size standard China National Standard (CNS) 8 4 specifications (210X297 mm) —- 1 ~ III '~ nn ^]. 1τΊ' II-(Please read the precautions on the back before filling in this Page) ~ Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Printed by the Shellfish Consumer Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs 406446 5. Production Instructions () 10 There is a cathode layer 15 with a transparent metal collection grid 14 ( Aluminum is used for the cathode) or a metal collection grid 13 (copper is used for the anode). The metal collection grid 13 is also coated with two layers of anode plastic 16. The collecting plate 20 is interposed between the anode layer and the cathode layer (15 and 16) to prevent short circuit of the battery. Typically, the 'anode element and the cathode element can be stacked into multiple layers, which are interposed between the surfaces without being sandwiched between layers. Clapboard. With a well-ordered configuration, the multi-layered single or double structure can be completed by traditional layering methods. The separator of the present invention does not chip under these circumstances, and the layer can be divided by a blade without causing its edges to collapse and cause a battery short circuit. Therefore, an unlimited change in the shape of the battery parts can be easily obtained. Because the layer has a high degree of permeability, the battery parts can be filled with electrolyte and buried in gelatin or other materials to block moisture and prevent electrolyte loss. This structured battery is a power source that can be used for many objects. Due to the repeated charging cycles required, the battery's life can be expected to be longer than or equal to the object using the battery. Another advantage of this system is that the use of the stable layering method of the present invention does not require auxiliary machinery, and the traditional battery metal case substantially increases the weight of the entire battery. By using the stable layered separator of the present invention, the structure itself can also be used as a battery case, so that the weight of additional parts can be prevented from increasing. In actual construction, small metal particles may protrude from the end of the layer to provide a connection point for the circuit. The common electrodes can be interconnected by conventional methods. Further advantages of the present invention will become clearer in the following examples. Example _______12 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm ^ (Please read the precautions on the back before filling this page) Order 406448 A7 B7

X Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () The manufacturing method of the separator according to the present invention is as follows: A non-woven polyethylene fiber-like substrate (Web Dynamix, Px0074) is purchased from the market. Its material manufacturing specifications include a thickness of 2.5 mil and a diameter of no more than 0.1 leg. Its products have a rough surface and another smooth surface. The density of the material is determined empirically as 28 g / m3. The manufacturer of these fiber sheets is STET, which is coated with complete rolls. The copolymer is coated by applying a coating of approximately 12 feet in length (a roll having a diameter of 12 inches) from the entire fiber sheet. The mixed coating contains 15g of Kynar brand 741 polyvinylidene fluoride copolymer, 30g of diethylsuccinate (as a plasticizer) 'and 150ml of reagent grade acetone. The mixture is heated to 70 ° in a closed container. C is used to melt the ingredients, and then cooled to room temperature. A section of the whole fiber sheet is placed on flat glass with its smooth—edge facing glass. Excess mixed paint (approximately 75ml) was poured out of the fiber sheet and evenly distributed on the surface by a roller. After air-drying, the fiber sheet was turned over and the coating solution was applied to the smooth surface. The coating weight is 100g. The base thickness is 2.5mil, and the coating thickness is about 3.0mil. Combination of separator and solid-state lithium battery produced by this method: The cathode includes 65% of LiMn204 (Chemetal) dispersed in the substrate, and its composition is almost the same as the copolymer coating of the separator. Plastic electrodes also contain 5.4% (Super-P brand) to improve conductivity. Both sides of the cathode sheet are laminated with a bulging metal-aluminum collecting plate element. The battery is assembled in a dual mode, which is arranged by the following rigorous sequence: a cathode element, a separator plate, an anode element, a second separator plate, and a second cathode element. Each component is rolled and melted into layers by a roller at full pressure. 13 The paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) " '~~~ * (Please read the precautions on the back before filling this page) -Equipped with * 11 line 'Consumption cooperation between employees of the Bureau of Standards and Loss of Standards of the Ministry of Economic Affairs Du printed 406446 A7 ___B7_____ 5. Difficulties () Achieving a continuous uniform bonding structure. Appropriate foil leads are soldered to the structure and left in a heated state to remove residual plasticizer. Bonded batteries are filled with electrolyte in a moisture-free environment. The composition of the electrolyte was 2 parts of ethylene carbonate, 1 part of dimethyl carbonate and 1 part of LiPFe. The completed electrolyte solution can be purchased from Mitsubishi Petrochemical Company, and then the entire battery is placed in a soft aluminized plastic case, which becomes an effective solvent and moisture barrier. The test of the battery disclosed below was carried out with a charge and discharge machine of Arbin Company in the United States. The charging cycle of the battery was 15 hours at a constant charge of 10 mA, and the voltage reached 4.3V. This 4.3V voltage is maintained constant for another 2 hours. After a two-hour rest period, the battery was discharged at 15 mA until the voltage dropped to 3.0V. In the second charge cycle, the current was increased to 47 mA over a period of 2 hours until the voltage returned to 4.3V. After equilibration, discharge to 3.GV at 190 mA, and after balancing, continue to reduce the battery in a series of successively reduced amps. Circle 2a is composed of various battery parameters. Figure 2b is a plot of voltage as a function of time. Figure 2c is a graph of charge-discharge current versus time. Figure 2 (1 is a graph of charge and discharge capacity versus the same period of time. Using this data, a meaningful curve is created in Figure 3, and these results indicate that 30% of the rated capacity of the battery is released at 2C rate, 80% of the rated capacity is released at a rate of 1 :. The conclusion can be drawn that the battery can be used completely at a discharge rate of 1C or less, and the charge and discharge cycle has been repeated for an additional 42 times. Product damage caused by board defects. Since then, we have repeatedly engaged in the production of this battery structure, and found that the electricity without defects and good performance _____14 This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) ( Please read the note on the back before filling in this page) Order — — 406448 A7 B7 V. Suppression Note () The pool can continue to be produced, but those partition plates made of traditional materials and designs The resulting battery structure is prone to product damage, and the lamination process is also prone to cracking and tearing of the separator, causing short circuits. (Please read the precautions on the back before filling this page) Order the Central Standards Bureau of the Ministry of Economic Affairs Employee consumption cooperation Du printed paper Of the applicable Chinese National Standard (CNS) A4 size (210X297 mm)

Claims (1)

A8 B8 C8 D8 406448 t Patent scope A solid-state battery, including: a case with most electrodes contained in the case, one with a carbon or lithium embedded anode and another ~ lithium metal oxide cathode; an electrolyte solution in the case The electrolyte solution contains a lithium metal salt capable of being ionized in an organic solvent, and the salt is dispersed in the organic solvent; a current collecting plate is electrically connected to the electrodes, and is interposed between and in contact with the electrodes to A partition plate is interposed between the electrodes and includes a fibrous central base block having a surface, and at least one surface of the central base block is coated with a porous polymer coating layer. 2. The battery according to item 1 of the scope of the patent application, wherein the fibrous center block combined with the porous polymer coating layer can sufficiently penetrate the ions in the electrolyte and discharge at least 30% of the capacity at a 2C rate. 3. A battery separator plate that can be interposed between an anode and a cathode, the battery separator plate includes: a porous core layer, the core layer has opposite surfaces, at least one surface of which has a porous polymer coating layer Applied to at least one surface of the fibrous central substrate. 4. A method for sub-assembly of a layered structure of a storage battery, wherein the sub-assembly of the storage battery includes an anode and a cathode, and a partition plate is interposed between the anode and the cathode, the method includes: orderly arranging into a A stack of carbon or other lithium insert anodes, a lithium metal oxide cathode, and a separator plate interposed between the carbon or other lithium insert anode and the lithium metal oxide cathode, and the separator The paper size of the clapboard is applicable to the Chinese National Standard (CNS) A4 specification (210X297). {Please read the "Notes on the back" before filling out this page.) A8 B8 40644 & _〇1__ VI. Application, patent scope includes a fibrous central base block with a surface, at least one surface of which is covered with a porous polymer coating, and the anode, cathode, and separator plate Layered, the method is to apply sufficient heat and pressure to bond the anode, cathode and separator into a unified structure. (Please read the note $ on the back before filling out this page.) Order Printed by the Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 standard (210X297 mm)