CN104600308B - Lithium ion battery negative electrode material and method for preparing membrane electrode thereof - Google Patents
Lithium ion battery negative electrode material and method for preparing membrane electrode thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000012528 membrane Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 title abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 65
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 21
- 229910011140 Li2C2 Inorganic materials 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 65
- 239000003643 water by type Substances 0.000 claims description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 22
- 239000011651 chromium Substances 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 22
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 13
- -1 polypropylene Polymers 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 5
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
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- 150000004676 glycans Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920001282 polysaccharide Polymers 0.000 claims description 5
- 239000005017 polysaccharide Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 108010001394 Disaccharidases Proteins 0.000 claims 1
- 150000002016 disaccharides Chemical class 0.000 claims 1
- 125000000185 sucrose group Chemical group 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000000269 nucleophilic effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229920000128 polypyrrole Polymers 0.000 description 22
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 150000003233 pyrroles Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 229960001031 glucose Drugs 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000005839 radical cations Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910013458 LiC6 Inorganic materials 0.000 description 2
- 102000004895 Lipoproteins Human genes 0.000 description 2
- 108090001030 Lipoproteins Proteins 0.000 description 2
- 229910018688 LixC6 Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- TUMHNKUORWLQBE-UHFFFAOYSA-N [C].[Ar] Chemical compound [C].[Ar] TUMHNKUORWLQBE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910020042 NbS2 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 239000012429 reaction media Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to battery negative electrode materials and aims at providing a lithium ion battery negative electrode material and a method for preparing a membrane electrode thereof. The method comprises the following steps: sequentially adding LiOH solution and pyrrole solution into a water-soluble carbon source material, stirring, reacting, and performing spray drying in air, thereby obtaining a precursor; and respectively calcining under the conditions of 200 DEG C, 600 DEG C and 900 DEG C in the argon atmosphere for 2 hours, thereby obtaining nitrogen-containing porous carbon material loaded Li2C2 powder. The product has the advantages of good thermal stability and high conductivity, so that the electrochemical dynamic performance of the negative electrode is improved, the electrode polarization is reduced, the speed capacity of a lithium battery is improved, and the cathode potential is flat. According to a thin-layer structure of the membrane electrode, the transmission distance of the lithium ion is greatly shortened, high current discharge is promoted, the nitrogen-containing porous carbon material has high conductivity and contains rich nucleophilic center, metal lithium dendrites during high current discharge can be avoided, the safety of the lithium ion battery is improved, and the product can be applied to an electric automobile to serve as a power battery.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery negative material and its membrane electrode, more specifically, this
It is bright to be related to, with Lithium hydrate, pyrroles and glucose as raw material, using spray drying presoma be prepared, by calcining obtain it is nitrogenous
Porous carbon materials support Li2C2As the method for lithium ion battery negative material, and supported based on nitrogenous porous carbon materials
Li2C2Method for preparing membrane electrode.
Background technology
Lithium ion battery has the advantages that lightweight, capacity is big, memory-less effect, thus has obtained commonly used.Now
Many digital equipments all employ lithium ion battery and make power supply.The energy density of lithium ion battery is very high, and its capacity is same
1.5～2 times of the Ni-MH battery of weight, and there is very low self-discharge rate, be that it extensively should without noxious substance
Major reason.Nineteen ninety Japan Nagoura et al. is developed into petroleum coke as negative pole, with LiCoO2For the lithium ion of positive pole
Battery：LiC6|LiClO4-PC+EC|LiCoO2.The same year.Moli and the big battery companies of sony two declare to release
The lithium ion battery of negative pole.1991, Sony energy technology company developed jointly a kind of with polysaccharide alcohol heat with battery unit
Solution carbon (PFA) is the lithium ion battery of negative pole.Lithium ion battery tradition negative material has graphite (C6), sulfide：TiS2、NbS2,
Oxide：WO3、V2O5、SnO2Deng.By taking graphite cathode material as an example, negative reaction in charge and discharge process：
C6+xLi++ xe==LixC6
When being charged to battery, there is lithium ion to generate on the positive pole of battery, the lithium ion of generation is transported through electrolyte
Move negative pole.And be in layer structure as the graphite of negative pole, the lithium ion for reaching negative pole is just embedded into graphite layers, forms embedding lithium
Compound (LixC6), embedded lithium ion is more, and charging capacity is higher.When discharging battery, in being embedded in graphite linings
Lithium ion is deviate from, and positive pole is moved back into again.The lithium ion that positive pole can be returned to is more, and discharge capacity is higher.
Must possess claimed below as the negative material of lithium battery：(1) lithium storage capacity is high；(2) lithium is in negative material
In embedded, deintercalation reaction it is fast, i.e., diffusion coefficient of the lithium ion in solid phase is big, in the mobile impedance of electrode-electrolyte interface
It is little；(3) existence of the lithium ion in electrode material is stablized；(4) in the charge and discharge cycles of battery, negative material volume becomes
Change little；(5) electron conduction is high；(6) negative material is not dissolved in the electrolytic solution.
The selection of negative material has a great impact to the performance of battery.At present cathode of lithium battery research and development is main
Concentrate on material with carbon element and the metal-oxide with special construction.Most commonly graphite electrode, because graphitic conductive is good, ties
Brilliant degree is higher, with good layer structure, is adapted to the embedded and deintercalation of lithium.And its intercalation potential is low and flat, can be
Lithium ion battery provides high stable running voltage, substantially：(vs.Li between 0.00～0.20V+/Li).Honda Company's profit
(heated with certain firing rate with the thermal decomposition product PPP-700 of poly-phenylene vinylene (ppv) (Polyparaphenylene-PPP)
PPP to 700 DEG C, and the thermal decomposition product that obtains of held for some time) used as negative pole, reversible capacity can exceed LiC6(372mAh/
g)。
Colourless oil liquid is presented under pure pyrrole monomer room temperature.Polypyrrole (PPy) is a kind of heterocycle conjugated type conductive polymer
Son, usually unformed black solid.Chemical polymerization process is one of the effective means for preparing polypyrrole.Polypyrrole is a kind of empty
Gas good stability, insoluble insoluble stable material.PPy structures have the conjugation knot that carbon-carbon single bond and carbon-carbon double bond are alternately arranged
Structure, double bond is made up of sigma electrons and pi-electron, and sigma electrons are fixed cannot be moved freely, and covalent bond is formed between carbon atom.
2 pi-electrons in conjugated double bond are not fixed on certain carbon atom, and they can be from a carbon atom indexing to another
On carbon atom, i.e., with the tendency extended on whole strand.Intramolecular pi-electron cloud overlap to form can band, be whole point
Son is total, therefore pi-electron is similar to the free electron in metallic conductor.In the presence of having electric field, the electronics for constituting π keys can edge
Strand movement.So, PPy can be conductive.
Chemical polymerization is by being aoxidized to monomer using oxidant or being had by metal in certain reaction medium
The mode that machine thing is coupled obtains being conjugated long-chain molecule and while completing a doping process.The synthesis technique of the method is simple, into
This is relatively low, is suitable to a large amount of productions.Product when polypyrrole is prepared using chemical method is generally solid polypyrrole powder, that is, be insoluble in
General organic solvent, mechanical performance is also poor to be difficult to be processed.The mechanism that synthesis polypyrrole product is：First, system is worked as
In have in the presence of oxidant, can be oxidized in the presence of oxidant in an electroneutral polypyrrole monomer molecule and lose one
Electronics, becomes radical cation.So latter two radical cation is collided in system and is combined into containing two cationes certainly
By the polypyrrole of dication two of base, dication now generates one in electroneutral two in system through disproportionation
Polypyrrole.Electroneutral two polypyrrole can be combined with each other with the radical cation in system and generate the cation of three polypyrroles again
Free radical, through disproportionation the polypyrrole of trimer is generated, and is gone round and begun again and has been ultimately generated the polypyrrole of long chain.
The content of the invention
The technical problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided a kind of lithium ion battery negative
The preparation method of material and its membrane electrode.The present invention with Lithium hydrate, pyrroles and water-soluble carbon source material as raw material, using spraying
Drying prepares presoma, and by calcining the nitrogenous porous carbon materials for obtaining Li is supported2C2As lithium ion battery negative material.
Li2C2With high storage lithium specific capacity, theoretical capacity is up to 1418mAh/g.It is 3.8 times of graphite.But Li during discharge and recharge2C2's
Change in volume is quite big.
To solve technical problem, the concrete scheme of the present invention is：
A kind of preparation method of lithium ion battery negative material is provided, the negative material is that nitrogenous porous carbon materials are supported
Li2C2, its preparation method comprises the following steps：
(1) 6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；
(2) 4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in 30mL deionized waters, LiOH solution is obtained；
(3) 5～50g water-soluble carbon source materials are added in 30mL deionized waters, adds the LiOH molten after stirring and dissolving
Liquid；The chromium solution is stirring evenly and then adding into, stirring reaction 2 hours obtains presoma after being spray-dried in atmosphere；(should
In step, pyrroles generates pyrroles's lithium with Lithium hydrate reaction, and pyrroles's lithium is by the oxygen in air in subsequent spray-drying process
Gas oxidation polymerization, forms polypyrrole lithium powder, and with carbon source material uniform mechanical impurity is formed, and obtains presoma)
(4) under an argon, the presoma is respectively calcined 2 hours under the conditions of 200 DEG C, 600 DEG C, 900 DEG C, is contained
Nitrogen porous carbon materials support Li2C2Powder；(in the step, carbon source material dehydration is calcined at 200 DEG C and occurs tentatively to be carbonized, 600 DEG C
Lower calcining polypyrrole lithium is cracked, and calcining at 900 DEG C obtains nitrogenous porous carbon materials and supports Li2C2)。
In the present invention, the water-soluble carbon source material is monosaccharide or polysaccharide；The monosaccharide is glucose, and the polysaccharide is sugarcane
Sugar, soluble starch or soluble cellulose.
Present invention also offers a kind of preparation method of lithium battery cathode plate, comprises the following steps：
(1) 6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；
(2) 4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in 30mL deionized waters, LiOH solution is obtained；
(3) 5～50g water-soluble carbon source materials are added in 30mL deionized waters, adds the LiOH molten after stirring and dissolving
Liquid；The chromium solution is stirring evenly and then adding into, continues stirring reaction 2 hours, then heating evaporation is until obtain thick half
Fluid；
(4) semifluid is coated to as on the copper film of base material of cathode, under argon atmospher successively 200 DEG C, 600 DEG C,
Each calcining 2 hours, obtain negative plate under the conditions of 900 DEG C.(calcine carbon source material dehydration at 200 DEG C to occur tentatively to be carbonized, 600 DEG C
Lower calcining polypyrrole lithium is cracked, and calcining at 900 DEG C obtains negative plate.)
Invention further provides the method for preparing membrane electrode using aforementioned negative plate, comprises the following steps：
(1) preparation of positive plate
Take positive electrode 0.1g, by positive electrode, acetylene black, Kynoar N-Methyl pyrrolidone solution, by matter
Amount compares 85: 10: 100 mixed grindings, is modulated into after paste and is coated in aluminium film；In 100Kg/cm after drying in the shade2Pressure under suppress
Molding, obtains positive plate；
In the N-Methyl pyrrolidone solution (NMP) of the vinylidene (PVDF), Kynoar and N- methylpyrroles
The mass ratio of alkanone is 5: 95, and the concentration of Kynoar is 5wt% in N-Methyl pyrrolidone；The positive electrode is
LiCoO2、LiMn2O4、LiNi1/3Co1/3Mn1/3O2Or LiFePO4；
(2) prepared by modified micropore polypropylene screen
At 60 DEG C, by the polyethylene oxide modified Li of 0.07g+Type perfluorinated sulfonic resin powder is dissolved in 2g N- crassitudes
Ketone solution, takes 0.5ml and drips on the microporous polypropylene membrane (city dealer) of a diameter of 19mm after stirring；It is vacuum dried at 60 DEG C
12 hours, obtain modified micropore polypropylene screen；
The polyethylene oxide modified Li+The preparation of type perfluorinated sulfonic resin：
Take 10g LiOH to add into the 20wt% perfluorinated sulfonic resins of 100mL (Nafion originates from E.I.Du Pont Company) solution,
After stirring 30 minutes, the LiOH of surplus is fallen in centrifugation, obtains Li+Type perfluor sulfoacid resin solution；Take Li+Type perfluorinated sulfonic acid tree
Lipoprotein solution 100mL, adds polyethylene glycol oxide (PEO, city dealer) and 50mL deionized waters that 2g molecular weight is 500,000g/mol, stirs
Mix 1 hour, obtain the modified Li of PEO+Type perfluor sulfoacid resin solution；After spray drying, polyethylene oxide modified Li is obtained+Type is complete
Perfluorosulfonic acid resin powder；
(3) prepared by membrane electrode
After modified micropore polypropylene screen is impregnated in the electrolytic solution into 24 hours, as barrier film；By positive plate and negative plate
Electrode material side forms sandwich structure with barrier film in opposite directions, obtains membrane electrode.
5th, the lithium battery prepared using membrane electrode described in claim 4, it is characterised in that the electrolyte of the lithium battery
It is：With LiPF6For solute, the mixed solution with dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), ethylene carbonate (EC) is
Solvent, the LiPF in electrolyte6Concentration be 1mol/L；In the mixed solution, dimethyl carbonate: Ethyl methyl carbonate: carbonic acid
The mass ratio of vinyl acetate is 1: 1: 1.
The principles illustrated of the present invention：
Li2C2Be in-situ preparation on nitrogenous porous carbon carbon wall, with very high activity, and nitrogenous porous carbon during discharge and recharge
Material supports Li2C2Constancy of volume.Nitrogen in porous carbon contains lone pair electrons becomes nucleophilic center, exists beneficial to Li ions during charging
It is uniformly distributed in porous carbon micropore, so as to greatly inhibit the generation of metal Li dendrite.Li2C2As the negative of lithium ion battery
Pole active material, in the micropore in nitrogenous porous carbon, occurs not forming point discharge in charging process, will not cause dendrite
Occur, the structure of stable negative pole, so as to improve the life-span of lithium ion battery.This point is filled in the high magnification for improving lithium ion battery
Discharge cycles life-span aspect shows especially prominent.So far, nitrogenous porous carbon materials Li is not supported into2C2As lithium from
The report of sub- cell negative electrode material.
Compared with prior art, the device have the advantages that：
The present invention utilizes Li2C2Characteristic with high storage lithium specific capacity, forms a kind of lithium ion battery negative of high power capacity
Material.The Li formed in nitrogenous porous carbon micropore2C2Be conducive to stablizing for electrode structure.The nitrogenous porous carbon materials of the present invention
Support Li2C2With good heat stability, the advantage of good conductivity, so as to improve the electrochemical kinetics performance of negative pole, reduce
Electrode polarization, improves the speed capabilities of lithium battery, and negative pole current potential is flat.The laminate structure of membrane electrode highly shortened lithium ion
Transmission range, be conducive to heavy-current discharge, the good electric conductivity of nitrogenous porous carbon materials and containing abundant nucleophilic center can
Avoid occurring metal Li dendrite during heavy-current discharge, improve the safety of lithium ion battery, can be applicable to electric automobile as dynamic
Power battery.
Description of the drawings
Fig. 1 is the 0.2C electric discharges of the flexible package thin lithium ion battery using different positive electrodes prepared in embodiment nine
Curve.
Fig. 2 is the 1C discharge and recharges of the flexible package thin lithium ion battery using different positive electrodes prepared in embodiment nine
Cycle performance.
Reference in figure is：1 uses LiNi1/3Co1/3Mn1/3O2For the battery discharge curve of positive electrode, 2 use
LiCoO2For the battery discharge curve of positive electrode, 3 use LiMn2O4For the battery discharge curve of positive electrode, 4 use
LiFePO4For the battery discharge curve of positive electrode.2-1 uses LiFePO4For the inducing capacity fading curve of the battery of positive electrode,
2-2 uses LiNi1/3Co1/3Mn1/3O2For the inducing capacity fading curve of the battery of positive electrode, 2-3 uses LiCoO2For positive electrode
Battery inducing capacity fading curve, 2-4 uses LiMn2O4For the inducing capacity fading curve of the battery of positive electrode.
Specific embodiment
Present invention will be described in detail below.
Embodiment one：Glucose prepares nitrogenous porous carbon materials and supports Li for carbon source2C2
6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；In 30mL
4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in deionized water, LiOH solution is obtained；In 30mL deionized waters
Add and add above-mentioned LiOH solution after the glucose monohydrate stirring and dissolving of 50g mono-, be stirring evenly and then adding into above-mentioned chromium solution；Stirring
Reaction 2 hours, obtains presoma after spray drying；
Under argon atmospher, respectively calcine 2 hours in 200 DEG C, 600 DEG C, 900 DEG C, obtain nitrogenous porous carbon materials and support Li2C2Powder
End.
Embodiment two：Sucrose prepares nitrogenous porous carbon materials and supports Li for carbon source2C2
6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；In 30mL
4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in deionized water, LiOH solution is obtained；In 30mL deionized waters
Add and add above-mentioned LiOH solution after 30g sucrose stirring and dissolving, be stirring evenly and then adding into above-mentioned chromium solution；Stirring reaction 2 is little
When, presoma is obtained after spray drying；
Under argon atmospher, respectively calcine 2 hours in 200 DEG C, 600 DEG C, 900 DEG C, obtain nitrogenous porous carbon materials and support Li2C2Powder
End.
Embodiment three：Soluble starch prepares nitrogenous porous carbon materials and supports Li for carbon source2C2
6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；In 30mL
4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in deionized water, LiOH solution is obtained；In 30mL deionized waters
Add and add above-mentioned LiOH solution after 10g soluble starch stirring and dissolving, be stirring evenly and then adding into above-mentioned chromium solution；Stirring is anti-
Answer 2 hours, presoma is obtained after spray drying；
Under argon atmospher, respectively calcine 2 hours in 200 DEG C, 600 DEG C, 900 DEG C, obtain nitrogenous porous carbon materials and support Li2C2Powder
End.
Example IV：Soluble cellulose prepares nitrogenous porous carbon materials and supports Li for carbon source2C2
6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；In 30mL
4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in deionized water, LiOH solution is obtained；In 30mL deionized waters
Add and add above-mentioned LiOH solution after 5g soluble cellulose stirring and dissolving, be stirring evenly and then adding into above-mentioned chromium solution；Stirring
Reaction 2 hours, obtains presoma after spray drying；
Under argon atmospher, respectively calcine 2 hours in 200 DEG C, 600 DEG C, 900 DEG C, obtain nitrogenous porous carbon materials and support Li2C2Powder
End.
Embodiment five：Soluble cellulose prepares lithium battery cathode plate for carbon source
6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；In 30mL
4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in deionized water, LiOH solution is obtained；In 30mL deionized waters
Add and add above-mentioned LiOH solution after 10g soluble cellulose stirring and dissolving, be stirring evenly and then adding into above-mentioned chromium solution；Stirring
Reaction 2 hours, heating evaporation is until obtain thick semifluid；Semifluid is coated to as on the copper film of base material of cathode,
Carbon source material dehydration is calcined at argon atmospher is lower 200 DEG C preliminary carbonization occurs, polypyrrole lithium is calcined at 600 DEG C and is cracked, 900 DEG C
Lower calcining obtains negative plate.
Embodiment six：PEO is modified Li+It is prepared by type perfluorinated sulfonic resin powder
Take 10g LiOH to add into 100mL perfluorinated sulfonic resins (Nafion) solution (20wt% originates from E.I.Du Pont Company),
After stirring 30 minutes, the LiOH of surplus is fallen in centrifugation, obtains Li+Type perfluor sulfoacid resin solution；By Li+Type perfluorinated sulfonic acid tree
Lipoprotein solution 100mL, adds 2g cities dealer's polyethylene glycol oxide (molecular weight is 500,000g/mol) and 50mL deionized waters, and stirring 1 is little
When, obtain the modified Li of PEO+Type perfluor sulfoacid resin solution, after spray drying, obtains the modified Li of PEO+Type perfluorinated sulfonic resin powder
End.
Embodiment seven：It is prepared by modified micropore polypropylene screen
At 60 DEG C, by the modified Li of the polyethylene glycol oxide (PEO) obtained in embodiment six+Type perfluorinated sulfonic resin powder
(0.07g) NMP (2g) is dissolved in, city's dealer's microporous polypropylene membrane that 0.5ml drips to a diameter of 19mm is taken after stirring, at 60 DEG C,
Vacuum drying obtains modified micropore polypropylene screen in 12 hours；
Embodiment eight：It is prepared by membrane electrode
6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；In 30mL
4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in deionized water, LiOH solution is obtained；In 30mL deionized waters
Add and add above-mentioned LiOH solution after 15g soluble starch stirring and dissolving, be stirring evenly and then adding into above-mentioned chromium solution；Stirring is anti-
Answer 2 hours, heating evaporation is until obtain thick semifluid；Semifluid is coated to as on the copper film of base material of cathode, in argon
Carbon source material dehydration is calcined at atmosphere is lower 200 DEG C preliminary carbonization occurs, polypyrrole lithium is calcined at 600 DEG C and is cracked, at 900 DEG C
Calcining obtains negative plate.
Take LiCoO20.1g, in mass ratio LiCoO2: acetylene black: the N-Methyl pyrrolidone of Kynoar (PVDF)
(NMP) solution, in mass ratio 85: 10: 100 mixed grindings, are modulated into after paste and are coated in aluminium film；In 100Kg/ after drying in the shade
cm2Pressure under it is compressing, obtain positive plate；In N-Methyl pyrrolidone (NMP) solution of Kynoar (PVDF),
The mass ratio of PVDF and NMP is 5: 95；
The modified micropore polypropylene screen obtained in embodiment seven is impregnated in the electrolytic solution 24 hours for barrier film, by positive plate
In opposite directions sandwich structure is formed with barrier film with the electrode material side of negative plate, obtain membrane electrode；Electrolyte is with LiPF6For solute,
With dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), (mass ratio is 1 to ethylene carbonate (EC):1:1) solution is solvent, electric
The LiPF of Xie Zhizhong6Concentration be 1mol/L.
Embodiment nine：It is prepared by flexible package thin lithium ion battery
6.7g (0.1mol) pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；In 30mL
4.2g (0.1mol) monohydrate lithium hydroxide stirring and dissolving is added in deionized water, LiOH solution is obtained；In 30mL deionized waters
Add and add above-mentioned LiOH solution after 25g sucrose stirring and dissolving, be stirring evenly and then adding into above-mentioned chromium solution；Stirring reaction 2 is little
When, heating evaporation is until obtain thick semifluid；Semifluid is coated to as on the copper film of base material of cathode, under an argon
Carbon source material dehydration is calcined at 200 DEG C preliminary carbonization occurs, polypyrrole lithium is calcined at 600 DEG C and is cracked, calcined at 900 DEG C
To negative plate.
Take LiFePO40.1g, by LiFePO4: acetylene black: the N-Methyl pyrrolidone (NMP) of Kynoar (PVDF) is molten
Liquid, in mass ratio 85: 10: 100 mixed grindings, are modulated into after paste and are coated in aluminium film；In 100Kg cm after drying in the shade-2Pressure
Under it is compressing, obtain positive plate；In N-Methyl pyrrolidone (NMP) solution of Kynoar (PVDF), PVDF and NMP's
Mass ratio is 5: 95；
The modified micropore polypropylene screen obtained in embodiment seven is impregnated in the electrolytic solution 24 hours for barrier film, by positive plate
In opposite directions sandwich structure is formed with barrier film with the electrode material side of negative plate, obtain membrane electrode；Electrolyte is with LiPF6For solute,
With dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), (mass ratio is 1 to ethylene carbonate (EC):1:1) solution is solvent, electric
The LiPF of Xie Zhizhong6Concentration be 1mol/L.
Membrane electrode is loaded in city's dealer's plastic-aluminum shell flexible package, anode and cathode terminals is drawn from positive plate and negative plate respectively, will
Plastic-aluminum shell flexible-packaging vacuum is encapsulated, and obtains flexible package thin lithium ion battery.
As positive electrode LiFePO4It is replaced into LiCoO2、LiMn2O4、LiNi1/3Co1/3Mn1/3O2, using equally making
Journey, is obtained the different flexible package thin lithium ion battery of voltage, and its charge-discharge performance is as shown in Figure 2.
Finally, in addition it is also necessary to it is noted that listed above is only specific embodiment of the invention.Obviously, the present invention is not limited
In above example, there can also be many deformations.One of ordinary skill in the art can directly lead from present disclosure
The all deformations for going out or associating, are considered as protection scope of the present invention.
Claims (5)
1. a kind of preparation method of lithium ion battery negative material, it is characterised in that the negative material is nitrogenous porous carbon materials
Support Li2C2, its preparation method comprises the following steps：
(1) 6.7g pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；
(2) 4.2g monohydrate lithium hydroxide stirring and dissolving is added in 30mL deionized waters, LiOH solution is obtained；
(3) 5～50g water-soluble carbon source materials are added in 30mL deionized waters, the LiOH solution is added after stirring and dissolving；Stir
The uniform rear addition chromium solution is mixed, stirring reaction 2 hours obtains presoma after being spray-dried in atmosphere；
(4) under an argon, the presoma is first calcined 2 hours at 200 DEG C, is then calcined 2 hours at 600 DEG C, finally existed
900 DEG C of conditions are calcined 2 hours, are obtained nitrogenous porous carbon materials and are supported Li2C2Powder.
2. method according to claim 1, it is characterised in that the water-soluble carbon source material is monosaccharide and disaccharide or polysaccharide；
The monosaccharide is glucose, and the disaccharidase is sucrose, and the polysaccharide is soluble starch or soluble cellulose.
3. the preparation method of lithium battery cathode plate, it is characterised in that comprise the following steps：
(1) 6.7g pyrrole monomer stirring and dissolving is added in 40mL deionized waters, chromium solution is obtained；
(2) 4.2g monohydrate lithium hydroxide stirring and dissolving is added in 30mL deionized waters, LiOH solution is obtained；
(3) 5～50g water-soluble carbon source materials are added in 30mL deionized waters, the LiOH solution is added after stirring and dissolving；Stir
The uniform rear addition chromium solution is mixed, continues stirring reaction 2 hours, then heating evaporation is until obtain thick semifluid；
(4) semifluid is coated to as on the copper film of base material of cathode, successively at 200 DEG C, 600 DEG C, 900 DEG C under argon atmospher
Under the conditions of each calcining 2 hours, obtain negative plate.
4. the method for preparing membrane electrode using negative plate described in claim 3, it is characterised in that comprise the following steps：
(1) preparation of positive plate
Take positive electrode 0.1g, by positive electrode, acetylene black, Kynoar N-Methyl pyrrolidone solution, in mass ratio
85: 10: 100 mixed grindings, are modulated into after paste and are coated in aluminium film；In 100Kg/cm after drying in the shade2Pressure under it is compressing,
Obtain positive plate；
In the N-Methyl pyrrolidone solution of the Kynoar, Kynoar is with the mass ratio of N-Methyl pyrrolidone
5: 95, the concentration of Kynoar is 5wt% in N-Methyl pyrrolidone；The positive electrode is LiCoO2、LiMn2O4、
LiNi1/3Co1/3Mn1/3O2Or LiFePO4；
(2) prepared by modified micropore polypropylene screen
At 60 DEG C, by the polyethylene oxide modified Li of 0.07g+It is molten that type perfluorinated sulfonic resin powder is dissolved in 2g N-Methyl pyrrolidone
Liquid, takes 0.5ml and drips on the microporous polypropylene membrane of a diameter of 19mm after stirring；It is vacuum dried 12 hours at 60 DEG C, obtains
To modified micropore polypropylene screen；
The polyethylene oxide modified Li+The preparation of type perfluorinated sulfonic resin：
Take 10g LiOH to add into the 20wt% perfluor sulfoacid resin solutions of 100mL, after stirring 30 minutes, centrifugation was fallen
Surplus LiOH, obtains Li+Type perfluor sulfoacid resin solution；Take Li+Type perfluor sulfoacid resin solution 100mL, add 2g molecular weight be
500,000g/mol polyethylene glycol oxide and 50mL deionized waters, stir 1 hour, obtain the modified Li of PEO+Type perfluorinated sulfonic resin
Solution；After spray drying, polyethylene oxide modified Li is obtained+Type perfluorinated sulfonic resin powder；
(3) prepared by membrane electrode
After modified micropore polypropylene screen is impregnated in the electrolytic solution into 24 hours, as barrier film；By positive plate and the electrode of negative plate
Material side forms sandwich structure with barrier film in opposite directions, obtains membrane electrode.
5. the lithium battery for being prepared using membrane electrode described in claim 4, it is characterised in that the electrolyte of the lithium battery is：
With LiPF6For solute, with dimethyl carbonate, Ethyl methyl carbonate, ethylene carbonate mixed solution as solvent, in electrolyte
LiPF6Concentration be 1mol/L；In the mixed solution, dimethyl carbonate: Ethyl methyl carbonate: the mass ratio of ethylene carbonate is
1∶1∶1。
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