TWI237643B - Method for manufacturing PAN polymer electrolyte used for isolation membrane of secondary battery - Google Patents

Abstract

The present invention is a crosslinked colloid compound electrolysis protoplasmic membrane used for an isolated membrane between anode and cathode, which is composed of PAN polymer electrolyte membrane, PVdF polymer and liquid electrolyte. Wherein, crosslinked PAN polymer electrolyte is polymerized from AN monomer and crosslinked monomer with two PANs on the end; PVdF homopolymer is PVdF-co-HFP copolymer with 80% PVdF; and liquid electrolyte is nonaqueous solvent composed of solving metals of alkaline or alkaline earth metal. The present invention has characteristics of excellent conductivity and mechanical intensity and well paste property with anode and cathode board and industrial potential.

Description

1237643 Case No. 9Π09990 Amendment V. Description of the invention 彳 1) The intermediate insulation film of the material of the present invention is made of cross-linked polymer and polyvinylidene fluoride, which has both high ion work and stick to the plate. Small and owned. Such hydrogen-producing batteries and even more and more lithium, 190.90%. Lithium ion secondary LiNi02 and other crystals Use porous PP to fill the separator. Ions pass from the positive electrode to the electrolyte through the crystal lattice. Discharger Lithium-ion binary density is the current potential. But the whole problem is due to the secondary colloidal yacry 1 polymer good mechanical point 'and the monthly changes, notepad prices make the industrial pool. The material used for electricity becomes Li Μ η. Graphite is used as the ion-separated ionic crystal lattice band to the negative mechanism. The state of the opposite capacitor battery. Electrolytic secondary battery refers to a kind of acrylonitrile (Polyethylene (PVdF)) with membrane structure. Special products with high degree of compatibility and good performance, such as the new mobile phones and the flattening of electronic prices, also drive the secondary charge of electric ions. In addition, in the early years, the positive powder of the battery, the negative mold of the battery, or the non-woven pores in the shape Lithium-ion battery and rechargeable secondary battery have the liquid used for the secondary use. This ion secondary battery is used as a composite electrolyte ο nitri 1 e, and liquid electric strength, process and no electrolyte can be carried around, digital Recorded more progress, the more the volume of the pool, the more environmentally friendly it will be lithium ion 02, Li Μ 204 or other irregular membranes, non-aqueous conductive pathways. Move out into the pole and enter the negative counter. Quantity , High voltage crown, the most fluid leakage will have to be sealed as a positive and negative membrane, this electrolyte PAN) gel electrolyte solution combination is simple and easy to add Missing concerns. The electronic products such as audio players can not only make it easier for consumers to record nickel batteries, the smaller the recording capacity, the better the capacitance. Commercialization of sub-batteries, Li C002, the obstacle to crystallization 'is a lithium salt electrolyte. Lithium electrolyte during the charging process, and then the advantages of extremely active materials, so it can be miniaturized and lightweight.

Page 7 1237643 Case No. 91109990 _Ά Name Amendment V. Description of the Invention (2) The case, which limits the possibility of miniaturization and thinning of lithium ion secondary batteries, so the concept of polymer batteries came into being. The so-called lithium polymer battery is to replace the separator of the traditional lithium ion secondary battery with a polymer electrolyte membrane that can absorb the electrolyte, so that the liquid electrolyte is absorbed by the electrolyte membrane without leaking out. In addition, the positive and negative electrodes are tightly connected by the adhesive characteristics of the polymer electrolyte membrane, which simplifies the assembly of the battery and makes the design more diverse. In the early 1980s, Armand et al. (U.S. Pat. No. 4303748, 1 981) proposed the idea of replacing polymer electrolytes with liquid polymer electrolytes in batteries. This type of polymer electrolyte is composed of a polymer and a lithium salt, and is called a solid polymer electrolyte. The polymer film used at that time was prepared by incorporating polyethylene oxide (PEO) and polyoxypropane (PPO) into alkaline gold or alkaline earth electrolyte salts. Although this solid polymer electrolyte membrane has quite excellent mechanical strength, its room temperature conductivity is quite low, making this electrolyte not applicable to general battery products. Although solid polymer electrolytes have been improved and improved by many researchers, they still cannot overcome the problem of low conductivity at room temperature (" Polymer Electrolytes ", Fiona M. Gray, 1997, pages 37-44). The problem of poor conductivity of the molecular electrolyte is the idea of adding a plasticizer to the polymer to increase the conductivity of the electrolyte membrane. This kind of polymer electrolyte containing electrolyte is called colloidal polymer electrolyte, which is different from solid polymer electrolyte. Chua et al. (U.S. Pat. No. 5240790, 1993) mixed PAN polymer with r-butyrolactone and lithium salt to form an electrolyte membrane with conductivity similar to that of a liquid electrolyte. But this electrolysis

Page 8 1237643 V. Description of the invention Case No. 91109990 (3) Years and months _correction The mechanical strength of the plasma membrane is not good, and it will soften above 50 ° C for a long time, which does not meet the needs of practical applications. American Engineering Engineering Company Luying Sun et al. (U.S. Pat. No. 5609974, 1997) proposed PAN, acrylic acid 2-ethoxy

After mixing three monomers of ethyl ethoxylate (2_eth〇xyethyl acrylate) and tri (ethylene glycol) dimethacrylate with the electrolyte, add an oxybisisonitrile (AIBN) initiator, The solution is then applied to form a film and then heated and polymerized to form a colloidal electrolyte membrane with a chemically crosslinked structure, which improves the disadvantage of high temperature softening of the PAN electrolyte membrane. However, the mechanical strength of this electrolyte membrane is not good, and its mechanical strength needs to be reinforced with a fibrous filler. In addition, the low viscosity of OH ++ is not conducive to coating and film formation, and the formed electrolyte membrane cannot be effectively combined with the positive and negative electrode plates, making the electrolyte membrane difficult to be automated in battery production.

Bell Communications Research, Gozdz et al. (Ϋ.S. Pat. No. 5418091; 5429891, 1995) proposed a porous colloidal electrolyte membrane based on polyvinylidene (PVdF) polymer, which can achieve high conductivity at the same time. Requirements and high mechanical strength. However, the polymer electrolyte membrane's ability to absorb the electrolyte at high temperature will decrease, and the process of film formation is complicated, which is not conducive to industrial production. Yi Yueben NEC Company Amano et al. (U.S. Pat. Ν〇 · 6235433 2 0 0 1) used PVdF to add acrylic acryl (acryl0yl) cross-linked rubber degraded prepolymer glue 'coated to film The prepolymer glue solution is polymerized by heating ~ =. The electrolyte membrane prepared in this way has both PVdF electrolysis awareness and the ability of the acrylic gel colloid electrolyte to absorb the electrolyte. 'But ‘thin stuff’,

1237643 Case No. 91109990 A_η Revision V. Explanation of the invention (4) Molecular solubility parameter ((5) is only 9 ~ 10, which is the same as two kinds of highly polar solvents commonly used in general lithium ion secondary batteries, ethylene carbonate (EC) 5 = 1 4. 7, propylene carbonate (PC) (5 = 1 3.3. The difference is far away. Therefore, the electrolyte membrane cannot absorb a large amount of electrolyte, the conductivity is low, and after a long period of use, electrolysis The liquid may be discharged from the electrolyte membrane. PAN polymer ((5 = 15.4) has similar solubility parameters with the two solvents of EC and PC. The electrolyte membrane made of PAN polymer has an ion conductivity of 4 X 1 0-3 Above S / cm, it is the highest among the current colloidal electrolytes (B. S cr 〇sati, C hem, Mater. V o 1. 5 3 8, page 6, 1994). Based on the above conventional techniques, it can be summarized as the following shortcomings : 1 · The liquid electrolyte used in lithium ion secondary batteries will leak, and it must be sealed in a tight metal case. 2 · The solid polymer electrolyte membrane has relatively low conductivity at room temperature. 3 · Colloidal polymer Electrolyte membrane: (1) Poor mechanical strength, high temperature Softening (2) Low viscosity is not conducive to coating film formation (3) Low ability to absorb electrolytes at high temperature (4) Complex film forming process (5) Low adhesion to the plates To solve the above problems, the present invention proposes a glue State composite polymer electrolyte membrane 'is a cross-linked PAN colloidal electrolyte as the absorber of the electrolytic solution. The cross-linked PAN electrolyte is made by copolymerizing AN monomer and cross-linker monomer with two terminal acrylate functional groups. The cross-linking agent monomer has two end acrylate functional groups with a lithium ion transport function and good compatibility with the electrolyte

Page 10 1237643 Case No. 91109990 Amendment V. Description of the invention (5) The ethylene glycol segment force is quite good and the molecular weight is more than 50%) to reinforce its organic colloidal composite electricity received in the above two (interpene uses a non-aqueous solvent, internal The purpose is a salt and the form (I) shows: connection, so the cross-linked colloidal PAN electrolyte can absorb the electrolyte, which can reach more than six times the weight of the polymer body. Add more than 1,000 PVdF polymer homopolymerization Or PVdF content 8 Polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP mechanical strength, to produce a decomposed film with good mechanical strength and electrical conductivity, the process is simple and has great industrial potential The liquid and state electrolytes in the interpenetrating network tratingnetw rk (IPN) formed by the adsorbed polymers (PAN and PVdF) are solvents: such as cyclic carbonates, non-cyclic carbonates, amidines Solvents, ether solvents, etc., dissolve gold test group or soil test group. The chemical structural formula of the cross-linked colloidal PAN electrolyte is as follows:

Structural formula 其中 (wherein R: a hydrocarbon group of 1 to 4 carbons, X = 1 to 1 0) With the present invention, each of the conventional techniques listed in the foregoing can be overcome

Page 111237643 Case No. 91109990 ___ η Amendment V. Description of Invention (6) Disadvantages are described in detail as follows: L i Μη〇0,, L i Cο0 'The positive electrode material of the secondary battery is L i Μ η 0 $ L i N i 02, etc .; the negative electrode material is lithium metal, lithium alloy, lithium ion intercalating substance, among which the lithium ion intercalating substance is graphite, irregularly crystalline carbon material. The conductive polymer positive electrode active materials of organic secondary batteries are: organic sulfur polymers (0 r g a η 〇 s u 1 f u r,

Organ〇sulfide Polymer),? Aniline (polyaniline),? Yan 11 Billow (P 0 1 y p y r r o 1 e) is a conductive polymer-conductive carbon black composite formed by chemical polymerization, electrochemical polymerization, or chemical polymerization on the surface of conductive carbon black or graphite. The above-mentioned positive and negative materials are powdery, so when making electrode plates, the active material powder needs to be bonded into a film by a binder. Common binders are polyvinyl fluorides such as PVdF and polytetrachloroethylene (PTFE). . The composite colloidal polymer electrolyte membrane of the present invention contains a PV d F polymer having good affinity with polyethylene fluoride. When the prepolymer glue is coated on the electrode electrode plate, the polymer chains of the two will form entanglement at the interface. The electrolyte membrane and the electrode plate have a good interface adhesion, and this adhesion surface will not be separated by immersion in the electrolyte. Generally, the separator of lithium-ion batteries does not have good characteristics of adhering to the electrodes. Therefore, it is necessary to use a metal case to encapsulate the external pressure to help the electrodes and the separator adhere to each other. The composite polymer electrolyte membrane in the present invention can be tightly bonded to the electrode electrode plate itself, and the electrolyte is absorbed by the PAN cross-linked polymer in the electrolyte membrane without leaking. The aluminum foil bag can be packaged into a card-shaped battery, which greatly reduces the battery. Weight and volume. For polymer electrolyte membranes with practical value, highly absorbed electricity

Page 121237643 Case No. 91109990 Amendment V. Description of the invention (7) The deliquescence ability and good characteristics are the processing characteristics of the electrolyte which can not prevent the electrolyte; simplify and reduce the electricity. It is compatible with PVdF polymer, electrode active material and electrode plate, so it has the characteristics of easy fabrication. The solid south oxide), for example, is composed of salt (D Polymer, 14, Po1ymer. J. 7) The conductivity of the helical high-complex dislocation compound electrolyte, and the cation can conduct electricity through and through the segment (G. Good mechanical properties, and good or bad interface with the electrode plate. High ability to absorb the electrolyte can improve conductivity leakage; good mechanical strength makes the electrolyte membrane have an excellent interface with the electrode. The production cost of the packaging pool makes the design of the battery more flexible. The polymer electrolyte membrane can only meet the first of the three characteristics, and rarely can have all three characteristics. The electricity of the present invention has a PAN polymer. Excellent electrolyte absorption capacity, excellent mechanical strength, and the close bonding of the electrolyte membrane by the homogeneity of the PVdF-based adhesive polyethylene fluoride in the electrolyte membrane. The above characteristics can be achieved in manufacturing and the packaging process is simple 2. The appearance design of the battery is more flexible. The electrolyte is generally composed of polyalkylene polyoxyethylene (PE0), polyoxypropane (PP0) and various basic gold. E. Fento n, JM Parker, PV Wright, 589, 1973; PV Wright, Br., 319, 1 975). Pure PEO is a regular and regular molecule with a crystallinity of 66%. When it is in the form of an alkali metal salt, The degree of crystallinity can be increased to 70%. The solid polymerizability depends on the movement of cations in the polymer amorphous region to achieve several -CH2CH20- (E0) segments of oxygen atoms interacting with each other, and the screw moves to move, so that Solid polymer electrolyte with Perterson, P. Jacobsson, L. Μ. Torell,

Page 13 1237643 Case number 91109990 Amendment V. Description of invention (8)

Electrochim. Acta, 37, 1495, 1992). However, the conductivity of this solid polymer electrolyte is not high, only about 10-8 S / cm, and it is close to the conductivity of the organic electrolyte at about 100 ° C, which is about 10-3 S / cm. There are practical application examples. Since the ionic system conducts electricity by moving in the amorphous region, how to reduce the crystallinity of polymers has become the focus of research. The colloidal polymer electrolyte has higher conductivity than the solid polymer electrolyte because it absorbs the electrolyte liquid in the polymer body. Because of the absorption of the electrolyte liquid, the soft colloidal polymer electrolyte has better adhesion to the positive and negative electrodes than the solid polymer electrolyte with a harder texture, and the interface resistance is also smaller. However, the colloidal polymer electrolyte also absorbs the electrolyte fluid, which causes its size stability and mechanical strength to be relatively reduced. At high temperatures or pressures, the electrolyte is likely to soften and cause short circuits in the battery. The polyacrylonitrile (PAN) system colloidal electrolyte system is one of the most widely studied colloidal electrolyte systems. Because the PAN polymer has a relatively large polarity, it has a fairly good compatibility with commonly used high-polarity non-aqueous solvent electrolytes, so the PAN colloidal electrolyte has high conductivity. The general production of PAN-based electrolyte is to dissolve the PAN polymer (molecular weight between 10,000-1,000,000) in a large amount of liquid electrolyte, add the added ingredients, heat and stir well, and apply the flow PAN solution while it is hot. After forming the film, the cooled PAN polymer film is in a colloidal state. Such colloidal electrolytes will be deformed due to high temperature or external force for a long time, and they have safety problems when used as battery isolation films. From the perspective of the application of polymer batteries, solid polymer electrolytes and colloidal polymer electrolytes each have their excellent mechanical strength and electrical conductivity.

Page 14 1237643 __Case No. 91109990 ____ V. Description of the invention (9) -§ ----- Disadvantages, and for those who are suitable for polymer electric ground to achieve a balance. For example, the polymer electrolyte of = must be in the main structure of the two polymer electrolytes, and the two types of these two electrolytes are on the main chain of the molecule, that is, high mechanical strength. The f-type polymer electrolyte can have both of the present invention. The advantages of colloidal recombination and conductivity are proposed. High mechanical strength, which can be applied to thin-molecule molecular electrolytes with high conductivity and secondary batteries, especially lithium polymer secondary batteries with large capacity and high output density. Polymer-free colloidal electrolyte used in pool-free Polymer-based colloidal electrolyte of the present invention # The molecular body and the non-aqueous electrolyte, and the shellfish are mainly made of polymers with a highly cross-linked structure with a cross-linked structure. Σσ _ The oxide is the starting zibu and is mixed with the addition of =: = crosslinking agent monomers, plus ~ + mesh guobu and a combination of thermal or light-induced co-polymerization and synthesis. Macromolecules without chemical cross-linking structure have better properties and better mechanical strength. Mix another parent molecule, such as polyvinylidene chloride (pvdF), polyethylene oxide (PEO), polystyrene (ps), etc., into the above monomer and crosslinker monomer mixture. After the mixed colloidal liquid is coated and then copolymerized to form a film, a mutual tooth network structure can be formed. By combining different polymer characteristics, the mechanical strength of the composite polymer can be further improved. In the present invention, a crosslinker monomer having two chains at both ends and a -ch2ch2o- segment in the middle is used, for example: ethylene glycol dimethacrylate (EGD), as shown in structural formula (II) Or triethylene glycol dimethacrylate (TGD), as shown in structural formula (III). selected

Page 15 1237643 Case No. 91109990 #: _ Amendment V. Explanation of the invention (10) The crosslinker monomer with the E 0 segment in the middle is selected because the unshared electron pair of the oxygen atom on the E 0 segment can interact with the oxygen ion The formation of coordination bonds can increase the dissociation degree of the positive and negative ions of the alkali metal salt. 〇 h3cv

ch2 〇 ch2 〇

CH, structural formula (II).

Non-aqueous electrolyte solution is composed of non-aqueous organic solvent and metal salt, which can be used as plasticizer. Non-aqueous organic solvent refers to an organic solvent with a high dielectric constant and a dipole distance sufficient to dissociate salts. It can be ethylene carbonate (EC), propylene carbonate (PC), butene carbonate (BC), dimethyl carbonate A mixed solution of cyclic and acyclic carbonates such as DMC, diethyl carbonate (DEC) and other organic solvents. Other organic solvents can be dimethyl ethane (DME), dimethyl formamide (DMF), dimethyl sulfene (DMSO), T-butyrolactone, N-methyltetrahydro 11 pylonone , Vinegar, internal vinegar and low molecular weight ether. Soluble in non-water soluble

Page 16 1237643 Case No. 91109990 ^ ____ η Revision V. Description of the invention (11) Liquid electrolyte used as ions LiPF6, LiSbF6, Li Li AsF6, LiCF3S03 2) 3C > Li (C2F5S02) 3 Non-aqueous production. Non-aqueous can be added at the same time. The colloids of the operators are divided into two electrolytes so that the colloids are more than 1M, which shows that the non-comprehensive reason is that in the pool, the combined electrolysis and the process are state composite steps. Solution absorption is used for voltage electrolysis, and it is not suitable for the current hair as a plasma membrane to reach the completion of electrolysis, and then the steps. The battery range and quality are described in a small arrangement with the lithium salt. Electrical, easy to the above-mentioned membrane, the metal salt of the conductor is: LiBF4, LiC104, I, LiBr, LiCl, LiA1C14, LiSCN, Li (CF3S02) 2N, Li (C2F5S02) 2N, Li (CF3S〇: etc., including lithium The degree of combination of salts that can conduct electricity within the salt is usually 0.2 to 0.3 M. The process of the sub-colloid electrolyte is simple, suitable for industrialized electrolyte solutions as monomer solvents, and the polymer is completed in the reverse polymerization step. State electrolyte preparation: Or firstly prepare the crosslinked polymer film and non-aqueous crosslinked polymer film to be immersed in the non-aqueous electrolyte solution. The electrolyte, whether liquid or colloidal, must be broad to ensure the stability of battery properties. The invention of the high-segment cross-linked PAN colloidal electrolyte is taken as an example. The decomposition voltage of the electrolyte at the absorption concentration is 5V (vs. Li / Li +). The application of secondary batteries. The invention does overcome all the shortcomings of conventional technology. The main purpose is to provide a crosslinked colloidal metathesis membrane used in the construction of an intermediate separator for secondary electrical negative electrode materials. The characteristics of mechanical strength processing and good adhesion to the electrode plate. The invention is realized as follows: a crosslinked rubber is composed of a crosslinked polyacrylonitrile (PAN) gel electrolyte,

Page 17 1237643 Case No. 91109990 Amendment V. Description of the Invention (12) Polyvinylidene fluoride (PV V d F) polymer is combined with liquid electrolyte, in which the crosslinked PAN electrolyte is made of AN monomer and has Cross-linker monomers of two terminal acrylate functional groups are copolymerized; polyvinylidene fluoride (PVdF) refers to a polymer homopolymer with a molecular weight of 5,000 or more, or a PVdF content of 80 % Polyvinylidene fluoride-hexafluoropropylene copolymer; liquid electrolyte uses non-aqueous solvents: such as cyclic carbonates, non-cyclic carbonates, ammonium solvents, lactone solvents, ether solvents It is formed by dissolving alkali metal or alkaline earth metal salts. The content of the electrolyte is 10% to 200% of the weight of the high molecular weight substrate in the electrolyte membrane, and the crosslinked colloidal composite polymer S / cm. In addition, the composite high-grade electrolyte membrane has a conductivity higher than lx 10 sub-electrolyte membranes. Polyethylene oxide (PEO) soft chain polymers or porous inorganic fillers can be added below 20% to increase its mechanical strength. In order to make your reviewers better understand the structural features and effects of the present invention, the following specific embodiments are used in conjunction with the accompanying drawings to make a detailed description of the present invention, which will be described later (used in the examples). The AN and cross-linker monomers were all treated with standard purification steps in advance to remove stabilizers. Example 1. Preparation of cross-linked polyacrylonitrile polymer membrane (without electrolyte). Take 0.5 g of PEO and add 4 g of DMF and 6 g of AN. In the monomer and 2 g of TGD, stir at a temperature of less than 50 ° C for about 6 hours until the solution is uniformly mixed, and then cool it at room temperature for use. After O.lg (Benzoly peroxide, BPO) was dissolved in 3 g of A N to form a transparent solution, it was added to the aforementioned mixed solution and slowly stirred at room temperature to form a homogeneous colloidal solution. Finally pour the resulting colloidal solution into the thickness

Page 18 1237643 _ Case No. 91109990_ Amendment 5 、 Explanation of invention (13) In a mold of about 15 0 ~ 2 5 0 // m, after capping, it is sent to an oven to heat and polymerize at 60 ° C. 1 2 hours. After the reaction is completed, the mold can be opened to obtain a crosslinked polyacrylonitrile polymer electrolyte dry film having a thickness of about 150 to 250 mm. Example 2: Preparation of cross-linked polyacrylonitrile polymer electrolyte membrane (containing electrolyte solution) 1.5 g of PEO was dissolved in 20 g of 1M LiC104 / EC / PC solution, heated and stirred to 100 ° C, and a uniformly mixed solution was obtained. , Cool at room temperature for future use. Take 0.15g of BPO, add 3.5g of AN and lg TGD and stir at room temperature, then pour into the above mixed solution, and stir at room temperature until a translucent colloidal solution is obtained. The colloidal solution was poured into a mold having a thickness of about 150 to 2500 // m, sealed and sent to an oven, and heated and polymerized at 60 ° C for 12 hours. After the reaction is completed, cross-linked PAN polymer electrolyte membrane with a thickness of about 150 to 250 // m can be obtained. Embodiment 3 Preparation of Crosslinked Colloidal PVdF-PAN Composite Polymer Electrolyte Membrane The manufacturing method of electrolyte colloidal solution containing AN monomer is as described in Embodiment 2. Dissolve 3g of PVdF in 10g of acetone, heat to 50 ° C with stirring, and cool to room temperature after dissolving uniformly. After adding electrolyte colloidal solutions of different weight ratios, stir slowly at room temperature until a homogeneous colloidal solution is obtained. The obtained colloidal solution was scraped on the stencil with a spatula (400 μm) to form a uniform film. The film was placed in a nitrogen-filled drying box for 12 hours. After removing most of the acetone, a semi-transparent film was obtained. Covered with glass and placed in an oven, heated and polymerized at 60 t for 12 hours. After the reaction is completed, a crosslinked 丨 ® PVdF-PAN composite electrolyte membrane with a thickness of about 15 0 to 2 50 # m can be obtained.

Page 19 1237643 Case No. 91109990 Amendment V. Description of the invention (14) Example 4 TGA analysis of crosslinked PAN electrolyte membrane and uncrosslinked PAN powder Example 1 Crosslinked PAN electrolyte membrane and uncrosslinked PAN powder respectively The thermal stability analysis was performed. The uncrosslinked PAN powder began to decompose at about 300 ° C, while the crosslinked PAN electrolyte dry film began to decompose at about 360 to 37 ° C. This is because the formation of a crosslinked structure makes the crosslinked PAN electrolyte membrane have relatively good thermal stability. Example 5 Swelling test The cross-linked colloidal PVdF-PAN composite polymer electrolyte membrane was swelled with diphenylmethylformamide (DMF), a good solvent for PAN, and acetone, a good solvent for PVdF, respectively. The test results are shown in Table 1. Table 1 Types of electrolyte membranes Observation results using PAN electrolyte membrane (uncrosslinked) Dimethylammonium chloride completely dissociates and crosslinked PAN electrolyte membrane (Example 1) Volume of amine swells but does not dissolve. ¥ Electrolyte membrane (Implementation II) Dimethyl T amine swells but does not dissolve PVdF porous membrane (uncrosslinked). Acetone completely dissolves PVdF-PAN composite polymer electrolyte membrane (Example 3) Although the acetone expands by volume but does not dissolve, the prepared electrolyte good solvent can diffuse into the example

Page 20 1237643 Case No. 91109990 Amendment V. Description of the invention (15) Inside the membrane, but because the polymer chains are linked to each other by chemical cross-linking, the solvent cannot further dissolve and dissolve the swollen molecular chains. Example 6. Absorbing Li C104 / EC / PC electrolyte solution of different concentration with cross-linked PAN electrolyte membrane. We use the electrolyte membrane of Example 1 to absorb LiC104 / EC / PC electrolytic solution with different concentration. After the surface is dried, weigh the cross-linked PAN. The weight of the electrolyte solution absorbed by the electrolyte membrane, and its conductivity was measured. The results obtained are summarized in Table 2. Because the PAN polymer has a relatively large polarity, it can absorb a large amount of electrolyte, and the more the amount of electrolyte absorbed, the higher the conductivity. Table 2 The electrolyte used is strongly crosslinked PAN electrolyte membrane Crosslinked PAN electrolyte membrane (M LiC104 in electrolyte absorption (conductivity (10.3 EC / PC (1/1)) multiples of dry film weight) S / cm) 0.5 6.35 2.15 1 6.11 2.02 1.5 5.4Q 1.51 2 5.61 1.3 Implementation Example 7: Electrochemical stability of crosslinked PAN electrolyte membrane The crosslinked PAN electrolyte membrane of Example 1 absorbed electrolytes of different salts: LiC104 (1 1), LiCF3S03 (1 2), LiBF4 (1 3), L After i PF6 (1 4), the results obtained by measuring its decomposition voltage are shown in Fig. 1. The experimental conditions are: absorption voltage of cross-linked PAN electrolyte membrane of different electrolytes, v. s L i + / L i, working Electrode is stainless steel sheet, corresponding electrode

Page 21 1237643 Case No. 91109990 Amendment V. Description of the Invention (16) Lithium metal with a scan rate of 50 m V / s. The resulting decomposition voltage results are summarized in Table 3. Regardless of the electrolyte used, the cross-linked colloidal P A N electrolyte membrane exhibits an electrochemical stability of more than 5 V, far exceeding the charging voltage of ordinary lithium secondary batteries by 4 V. Table 3 Type of electrolyte (EC / PC (1/1)) Decomposition voltage (V, vs_ Li / Li +) 1 ML1CIO4 5.2 1 ML1CF3SO3 5.4 1 M LiBF4 6.3 1 Μ LiPF6 > 6.5 * Example VIII, Crosslinked colloidal state TGA Analysis and Conductivity Measurement of PVdF-PAN Composite Polymer Electrolyte Membrane The PVdF-PAN composite colloidal electrolyte membrane synthesized in Example 3 has different absorption capacities of the electrolyte with the two polymer components. Thermogravimetric analyzer) analyzes the electrolyte absorption of composite films with different components. The composition of the composite electrolyte membrane, the amount of electrolyte absorption, and the electrical conductivity are summarized in Table 4. Table 4

Absorption ratio of composite film component to electrolyte (conductivity (10.3 S / cm PVdF: PAN%)) 1: 1 50 0.6 1: 2 55.5 1.2 1: 3 63.5 1.9 Page 22 1237643 Case No. 9Π09990 A_ Modification V. Description of the invention (17) Example IX. Polyphenylene will be used as a lithium metal to gather polyaniline carbon black (see figure 2), PVdF-PAN foil (2 4), and figure 3 shows the amount before the battery 2) before the end of the cycle and about 99%. PV d F-PAN amine secondary battery with aniline battery composite electrolyte, negative 2 0 1 6 composite electrolyte gasket (2 5 30 cycles (3 1) no obvious decay composite colloidal electrolyte The film is used as a lithium metal poly-isolating film, which is a cross-linked colloidal PVdF-PAN insulating film. The electrode material is a chain metal, button-type battery, which is composed of positive (2 2), rubber washer), and spring (2 6 capacitance pair cycle). The number has reached stability until the situation of three retreats. The relationship diagram of the positive electrode structure material ((23)) of the Coulomb-effect composite electrolytic cell, the ten cycle rates always maintain the quality of the membrane material such as No. 2 and Li. No. Capacitor ( 3 Holding in Example 10, the cross-linked PVdF-PAN composite electrolyte membrane as a lithium ion secondary battery will absorb sufficient amount as the lithium ion secondary L i Mn2O4, the characteristics of the negative electrode material capacitance to the cycle number pool, especially the next more In order to be significant, for example, the function of the plasma membrane as a lithium ion discharge is determined, and the cell-stealing efficiency separator membrane electrolyte battery separator is a metal-to-metal relationship diagram, which is shown in the southern current diagram. capacitance As the amount is maintained at 9 9-linked colloidal PVdF-PAN composite electrolyte membrane, the positive electrode material of the battery is as shown in Figure 4. The capacity of the first thirty cycles of the battery has a decline in capacity. 5 C) Charging and discharging conditions The cross-linked PVdF-PAN composite electrolytic isolation film of the present invention can maintain the increase in the number of charge and discharge cycles of the battery to gradually stabilize to about%.

1237643 ___Case No. 91109990_Year of the month_Amendment__ V. Description of the invention (18) Example 11: Cross-linked colloidal PVdF_PAN composite electrolyte membrane as the separator of carbon negative polyaniline secondary battery, such as the battery of Example 9 Structure, the positive electrode material is a polyaniline carbon black composite. The negative electrode material is a MCMB carbon material with sufficient clock ions embedded, and the separator is a cross-linked PVdF-PAN composite electrolyte membrane. Figure 5 shows the relationship between the capacity and the number of cycles in the first forty cycles of the battery. The capacity has stabilized within five cycles (5 1), and there is no obvious decline until the end of the forty cycles (5 2). , Its Coulomb efficiency has been maintained at about 99%. Example 12: Lamination of Crosslinked Colloidal PVdF — PAN Composite Electrolyte Membrane and Lic002 Positive Electrode and MCMB Carbon Negative Electrode On: LiCo02 positive electrode plate and bonded with MCMB carbon negative electrode, placed in a nitrogen-filled dry box (nitrogen must remove water and oxygen) to volatilize and remove acetone. Finally, the AN monomer and the crosslinking agent monomer in the film were copolymerized into a crosslinked colloidal PAN electrolyte by heating at 60 ° C for 12 hours. After the above process, a three-layer structure of Lic00 positive electrode, cross-linked colloidal PVdF-PAN composite electrolyte membrane, and M CMB carbon negative electrode can be obtained. The tightness between the three layers of material is much greater than that of the electrode active material. The bonding force with the metal of the current collecting layer ', so external force pulling the bonding surface will cause the active material and the current collecting layer to peel off. Scanning electronic microscopy (SEM) was used to observe the cross-section of the three-layer structure. The results are shown in Figure 6. The upper layer of j4 | is a LiCo02 positive electrode (6 1), the middle layer is a cross-linked PVdF-PAN composite electrolyte membrane (62), The lower layer is an M CMB carbon negative electrode (6 3).

Page 24 1237643 Case No. 91109990 Modification Brief Description of the Drawings Figure 1 shows the experimental results of the decomposition voltage of the cross-linked P A N electrolyte membrane absorbing different electrolytes. Figure 2 shows the structure of a 2016 button-type battery containing a PVdF-PAN composite electrolyte membrane. Fig. 3 is a graph showing the relationship between the capacitance and the number of cycles when a PVdF-PAN composite electrolyte membrane is used as a separator of a lithium metal polyaniline secondary battery. Fig. 4 is a graph showing the relationship between the capacity and the number of cycles when a PVdF-PAN composite electrolyte membrane is used as a separator for a lithium ion secondary battery. Fig. 5 is a graph showing the relationship between the capacitance and the number of cycles when a PVdF-PAN composite electrolyte membrane is used as the separator of a carbon negative polyaniline secondary battery. Figure 6 is a cross-sectional view of a three-layer structure of a LiCo02 positive electrode, a cross-linked PVdF-PAN composite electrolyte membrane, and a MCMB carbon negative electrode. Brief description of drawing number: 1 2 14 2 2 2 4 2 6 3 2 5 2 6 2 • LiCF3S03 —— LiPF & • Composite electrolyte • • • Lithium foil Composite electrolyte membrane 1 1 · · · · LiC104 1 3 —— · · LiBF4 2 1 · · · cathode material 2 3 · · · rubber gasket 2 5 ..... gasket five cycles within five cycles LiCo〇2 cathode 6 3MCMB carbon anode

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Claims (1)

1237643 Case No. 91109990 said Amendment 6. Scope of patent application LiSbF6, LiI iLiBr, LiCl, LiA1C14, LiSCN, LiAsF6, LiCF3S03, Li (CF3S02) 2N, Li (C2F5S02) 2N, Li (CF3S02) 3C, Li (C2F5S02) 3C, among which the solvents used in the liquid electrolyte are cyclic carbonates, non-cyclic carbonates, ammonium solvents, lactone solvents, ether solvents, Among them, the solvents used in the liquid electrolyte are ethylene carbonate, propylene carbonate, butene carbonate, dimethyl carbonate, diethyl carbonate, dimethoxyethane, and dimethylformamide. , Dimethyl isocyanate, τ-butyrolactone, N-methyltetrahydropyrrolidone 2 34 The secondary battery according to item 1 of the patent application scope, wherein the electrolyte content in the crosslinked colloidal composite electrolyte membrane is 10% to 200% of the weight of the polymer substrate in the electrolyte membrane. For example, the secondary battery of item 1 of the patent application scope, wherein the conductivity of the cross-linked colloidal composite electrolyte membrane is higher than 10-4 S / cm. The secondary battery of item 1 of the patent application scope, wherein the cross-linking agent alone The body has the following structure: Page 27 1237643 Case No. 91109990 _Ά Amendment Scope of patent application Degradation and adhesion 6 · If the patent is applied > -PVdF homopolymer Hexafluoropropane 7 · If you apply for a special electrolyte polymer. 8 · If you apply for special electrolyte 9 · If you apply for special electrode cathode material ene nitrile gel electrolyte, you can add less than 15% acrylic acid, lithium acrylate more than one monomer, and copolymerize to give crosslinked PAN colloidal electricity . Please apply for a secondary battery under item 1 of the patent, in which the polymer of ethylene (PVdF) is a substance having a molecular weight of 5,000 or more or a polyvinylidene fluoride-copolymer (PVdF-co- HFP). The secondary battery of item 1 of the profit range, in which the composite high-resolution film can add less than 20% of the polyepoxy soft chain composite high-resistance conductive secondary charge range of the secondary battery, in which the film can be added with porosity Inorganic filler. The secondary battery according to item 1, wherein the material is in a doped state or an undoped state. % Page 28