CN106997965A - A kind of preparation method of new type lithium ion battery - Google Patents
A kind of preparation method of new type lithium ion battery Download PDFInfo
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- CN106997965A CN106997965A CN201710253463.2A CN201710253463A CN106997965A CN 106997965 A CN106997965 A CN 106997965A CN 201710253463 A CN201710253463 A CN 201710253463A CN 106997965 A CN106997965 A CN 106997965A
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- Prior art keywords
- lithium ion
- ion battery
- preparation
- new type
- nickel foam
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 45
- 239000006260 foam Substances 0.000 claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- 239000002070 nanowire Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 230000004888 barrier function Effects 0.000 claims abstract description 17
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 claims description 18
- 239000002608 ionic liquid Substances 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 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 14
- 239000011530 conductive current collector Substances 0.000 claims description 14
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000010306 acid treatment Methods 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 150000003863 ammonium salts Chemical group 0.000 claims description 6
- 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 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011381 foam concrete Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 238000011049 filling Methods 0.000 abstract description 8
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000003491 array Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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- Composite Materials (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation method of new type lithium ion battery, detailed process is：First using the method for co-precipitation, using nickel foam as matrix, the iron phosphate lithium positive pole piece of carbon coating is prepared；Then using nickel foam as substrate, Co3O4 nano-wire arrays are grown, and use the method for constant pressure electro-deposition in Co3O4 nano-wire arrays surface deposited silicon layer, and carbon-coating is sprayed in silicon surface, negative plate is made, finally positive plate, barrier film, negative plate is sequentially overlapped, the volume heart is made, it is sealed in battery container, injects electrolyte, preliminary filling, aging, chemical conversion, lithium ion battery energy density made from lithium ion battery this method is made high, power is big, good cycle, prepares cost low.
Description
Technical field：
The present invention relates to the preparation field of battery, a kind of preparation method of new type lithium ion battery is specifically related to.
Background technology：
Into 21 century, under world's energy scarcity and the macroscopic of environmental pollution, many countries will develop new
The type energy (wind energy, water energy, ocean energy and solar energy etc.) is proposed clearly as the important component of energy strategy
New energy developing goal, but the electric energy storage technology using lithium battery as representative constrains the application of new energy, therefore, prepares
Large Copacity, low cost, long-life and safe lithium ion battery, are the emphasis of current lithium ion battery industry development.
Lithium battery relies primarily on Li+Insertion between both positive and negative polarity active material carrys out work with deintercalation, during charging, Li+From
Deintercalation in positive-active compound, by electrolyte and barrier film, rich lithium state is presented in embedded negative pole lattice, negative pole, while in order to tie up
The balance of electric charge is held, the electronics of equal quantities is migrated to negative pole through external circuit by positive pole；During electric discharge, Li+From negative active core-shell material
Deintercalation, by electrolyte and barrier film, embedded positive pole, while the electronics of equal quantities is migrated to positive pole through external circuit by negative pole, it is this
Li+Insertion between both positive and negative polarity active material generates electric current with deintercalation process, realizes the charge and discharge electric work of lithium ion battery
Energy.Due to Li+There is relatively fixed position and space, therefore the reversibility of lithium ion battery in both positive and negative polarity active material
Well, and in charge and discharge process lithium metal is not present, the formation condition of Li dendrite is eliminated, it is ensured that the circulation of lithium battery
Performance and security performance.
Certainly, lithium ion battery is there is also some shortcomings, and such as fast charge-discharge performance is poor, heavy-current discharge performance not Dali
Think, the problems such as internal driving is higher.The performance of lithium ion battery material determines the performance of lithium ion battery to varying degrees
It is whether good.Wherein influence maximum is positive and negative pole material, and they are the key factors for improving performance of lithium ion battery.Therefore
The lithium rechargeable battery of excellent performance is made, first has to prepare the excellent lithium ion battery plus-negative plate material of electric property.
The content of the invention：
It is an object of the invention to provide a kind of hungry preparation method of new type lithium ion battery, lithium-ion electric made from this method
Pond charge/discharge capacity first is big, good cycling stability, excellent combination property.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of new type lithium ion battery, comprises the following steps：
(1) using nickel foam after low-kappa number as conductive current collector, by source of iron, phosphorus source, glucose be dissolved in water be made it is mixed
Solution A is closed, Quadrafos is added, obtained mixed solution B is well mixed, precipitating reagent is dissolved in into water is made precipitant solution, will steep
Foam nickel is added in reactor, then while mixed solution B, precipitant solution are added in reactor respectively, and co-precipitation is anti-
3-7h is answered, obtained product washing obtains iron phosphorus presoma after drying；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after high temperature sintering tabletting, cut into slices
To LiFePO4Positive plate；
(3) it regard nickel foam as conductive current collector after low-kappa number；Cobalt nitrate, urea and ammonium fluoride and water are mixed equal
Mixed liquor, is then transferred in reactor by even obtained mixed liquor, and adds the nickel foam of acid treatment obtained above；Heating is anti-
Should, room temperature is cooled to after the completion of reaction, obtained solid product washing is dried, Co is made in high-temperature calcination3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer
Linear array is classified as negative electrode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from
Sub- liquid, obtains the Co for having silicon layer to surface3O4Nano wire, finally carries out surface spray C processing, dries, tabletting, negative plate is made；
(5) positive plate, barrier film, negative plate are sequentially overlapped, the volume heart are made, is sealed in battery container, inject electrolyte,
Preliminary filling, aging, chemical conversion, are made lithium ion battery.
As the preferred of above-mentioned technical proposal, in step (1), the addition of the Quadrafos is phosphorus source, source of iron and Portugal
The 5-10% of grape sugar gross weight.
As the preferred of above-mentioned technical proposal, the concrete operations of low-kappa number nickel foam are：Nitre by nickel foam 30%
5min is soaked in aqueous acid.
As the preferred of above-mentioned technical proposal, in step (1), the adding speed difference of mixed solution B and precipitant solution
For：1-5 ls/h, 0.8-2.6 ls/h.
As the preferred of above-mentioned technical proposal, in step (3), the preparation method of the mixed liquor is specially：By 1-3g nitre
Sour cobalt, 0.3-0.5g ammonium fluorides and 1-3g urea are dissolved in 50mL distilled water, are slowly stirred 30min.
As the preferred of above-mentioned technical proposal, in step (3), the temperature of the heating response is 110-130 DEG C, reaction
Time is 1-5h.
As the preferred of above-mentioned technical proposal, in step (3), the condition of the high-temperature calcination is：Calcined at 350-450 DEG C
1-4h。
As the preferred of above-mentioned technical proposal, in step (4), the condition of the constant pressure deposition is：The direct life prepared
The Co of long nickel foam3O4Nano-wire array contains 0.25M SiCl as inert anode as negative electrode, Pt nets electrode at 50 DEG C4
Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, the time is 1-5h.
As the preferred of above-mentioned technical proposal, in step (5), the barrier film be by nano aluminium oxide and micrometer alumina with
And pore creating material mixing, the obtained multiaperture pellumina of secondary high-temperature sintering, its thickness is 80-120 μm, and pore size is 100-
300nm。
As the preferred of above-mentioned technical proposal, in step (2), the temperature of the high temperature sintering is 720-960 DEG C, and the time is
30-120min。
LiFePO4Exist in nature in the form of fosfosiderite, belong to olivine-type structure, be rhombic system, space group
For Pnmb.Wherein O atom is arranged in the tightly packed mode of six sides being slightly mispositioned, and Li is filled in octahedral interstices with Fe atoms,
Form FeO6And LiO6Octahedron, P occupies tetrahedron space, forms PO4Tetrahedron.One FeO6Octahedra and two eight LiO6
Face body and a PO4Tetrahedron is connected with common side；One PO4Tetrahedron is also with deforming octahedron FeO6And LiO6Common side.In FeO6
Layer ask, adjacent LiO6Two O atoms on the shared rib of octahedron, are connected and form three-layer laminated structure, be conducive to Li+
Abjection and insertion in charge and discharge process.And LiFePO4It is converted into FePO4Volume only reduces 6.81%, and negative material is filling
Volume can become big in discharge process, and the cumulative volume for so allowing for whole inside battery is varied less, therefore the positive electrode has
There is good cycle performance.But due to the FeO of corner-sharing in olivine structural6Octahedral to exist, it is low to reduce its electrical conductivity, thus
Cause LiFePO4Electric conductivity and high rate performance it is poor.The present invention, as substrate, is directly prepared using nickel foam on its surface
Positive electrode, and carbon modification is carried out, cost, and the electric conductivity of positive electrode have been saved in the addition for eliminating conductive agent and binding agent
It can be effectively improved.
Co3O4 nano wires as lithium ion battery negative material when first irreversible capacity it is larger, the rate of decay is very fast,
The present invention grows Co3O4 nano-wire arrays as substrate first using nickel foam, then using ionic liquid as electrolyte, is received in Co3O4
Nanowire arrays surface constant pressure deposits one layer of silicon layer, finally sprays C processing, and obtained negative material electric conductivity is high, and specific capacity is big, circulation
Stability is good.
Compared with prior art, the present invention has advantages below：
The present invention prepares positive electrode using the method for co-precipitation, before coprecipitation reaction, and the present invention is in reactant
Mixed liquor in add Quadrafos, its can with iron, phosphorus formation complex compound, effectively control its precipitation speed so that system
The positive electrode tap density obtained is big, and Quadrafos and iron, the complex compound of phosphorus formation are more stable, will not also change the acid of solution
Alkalescence, the cladding of carbon layer on surface effectively increases the electric conductivity of positive electrode, and using nickel foam as base during present invention co-precipitation
Bottom, its specific surface area is big, can improve the quality of active material, and eliminates the addition of binding agent and conductive black etc., saves
Cost；
When preparing cell negative electrode material, the present invention is first using nickel foam as substrate, in its superficial growth Co3O4 nano wires
Array, then using ionic liquid as electrolyte, deposits one layer of silicon layer, relative to original collosol and gel legal system in its surface constant pressure
Standby silicon layer, this method avoid organic solvent it is a large amount of using and solvent volatilization problems, safer environmental protection, obtained silicon layer is
Unformed silicon, surface easily generates layer of silicon dioxide, effectively inhibits the Volume Changes of Si in charge and discharge process so that this is born
Pole material electrochemical performance is more preferable.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of new type lithium ion battery, comprises the following steps：
(1) nickel foam will be soaked as conductive current collector after 5min, by source of iron, phosphorus in 30% aqueous solution of nitric acid
Source, glucose are dissolved in water and mixed solution A are made, and add Quadrafos, be well mixed obtained mixed solution B, precipitating reagent is dissolved in
Precipitant solution is made in water, and nickel foam is added in reactor, then while respectively adding mixed solution B, precipitant solution
Enter into reactor, coprecipitation reaction 3-7h, obtained product washing obtains iron phosphorus presoma after drying；Wherein, Quadrafos
Addition be phosphorus source, the 5% of source of iron and glucose gross weight；The adding speed of mixed solution B and precipitant solution is respectively：
1 l/h, 0.8 l/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, at 720 DEG C sinter
100min, tabletting, section obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam being soaked into 5min in 30% aqueous solution of nitric acid；By 1g cobalt nitrates,
0.5g ammonium fluorides and 1g urea are dissolved in 50mL distilled water, be slowly stirred 30min and mixed liquor is made, then shift mixed liquor
To reactor, and add the nickel foam of acid treatment obtained above；Reacted at 110 DEG C and be cooled to room after the completion of 5h, reaction
Temperature, obtained solid product washing is dried, Co is made in calcining 4h at 350 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer
Linear array is classified as negative electrode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from
Sub- liquid, obtains the Co for having silicon layer to surface3O4Nano wire, finally carries out surface spray C processing, dries, tabletting, negative plate is made；Its
In, the condition of constant pressure deposition is：The Co of the direct growth nickel foam prepared3O4Nano-wire array is made as negative electrode, Pt nets electrode
For inert anode, contain 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, when
Between be 1h；
(5) positive plate, barrier film, negative plate are sequentially overlapped, the volume heart are made, is sealed in battery container, inject electrolyte,
Preliminary filling, aging, chemical conversion, are made lithium ion battery.
Wherein, barrier film is that, by nano aluminium oxide and the mixing of micrometer alumina and pore creating material, secondary high-temperature sintering is obtained
Multiaperture pellumina, its thickness is 80 μm, and pore size is 100nm.
Embodiment 2
A kind of preparation method of new type lithium ion battery, comprises the following steps：
(1) nickel foam will be soaked as conductive current collector after 5min, by source of iron, phosphorus in 30% aqueous solution of nitric acid
Source, glucose are dissolved in water and mixed solution A are made, and add Quadrafos, be well mixed obtained mixed solution B, precipitating reagent is dissolved in
Precipitant solution is made in water, and nickel foam is added in reactor, then while respectively adding mixed solution B, precipitant solution
Enter into reactor, coprecipitation reaction 3-7h, obtained product washing obtains iron phosphorus presoma after drying；Wherein, Quadrafos
Addition be phosphorus source, the 10% of source of iron and glucose gross weight；The adding speed difference of mixed solution B and precipitant solution
For：5 ls/h, 2.6 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, sinter 30min at 960 DEG C,
Tabletting, section obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam being soaked into 5min in 30% aqueous solution of nitric acid；By 3g cobalt nitrates,
0.3g ammonium fluorides and 3g urea are dissolved in 50mL distilled water, be slowly stirred 30min and mixed liquor is made, then shift mixed liquor
To reactor, and add the nickel foam of acid treatment obtained above；Reacted at 130 DEG C and be cooled to room after the completion of 1h, reaction
Temperature, obtained solid product washing is dried, Co is made in calcining 1h at 450 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer
Linear array is classified as negative electrode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from
Sub- liquid, obtains the Co for having silicon layer to surface3O4Nano wire, finally carries out surface spray C processing, dries, tabletting, negative plate is made；Its
In, the condition of constant pressure deposition is：The Co of the direct growth nickel foam prepared3O4Nano-wire array is made as negative electrode, Pt nets electrode
For inert anode, contain 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, when
Between be 5h；
(5) positive plate, barrier film, negative plate are sequentially overlapped, the volume heart are made, is sealed in battery container, inject electrolyte,
Preliminary filling, aging, chemical conversion, are made lithium ion battery.
Wherein, barrier film is that, by nano aluminium oxide and the mixing of micrometer alumina and pore creating material, secondary high-temperature sintering is obtained
Multiaperture pellumina, its thickness is 120 μm, and pore size is 100nm.
Embodiment 3
A kind of preparation method of new type lithium ion battery, comprises the following steps：
(1) nickel foam will be soaked as conductive current collector after 5min, by source of iron, phosphorus in 30% aqueous solution of nitric acid
Source, glucose are dissolved in water and mixed solution A are made, and add Quadrafos, be well mixed obtained mixed solution B, precipitating reagent is dissolved in
Precipitant solution is made in water, and nickel foam is added in reactor, then while respectively adding mixed solution B, precipitant solution
Enter into reactor, coprecipitation reaction 3-7h, obtained product washing obtains iron phosphorus presoma after drying；Wherein, Quadrafos
Addition be phosphorus source, the 7% of source of iron and glucose gross weight；The adding speed of mixed solution B and precipitant solution is respectively：
2 ls/h, 1.2 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, at 750 DEG C sinter
120min, tabletting, section obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam being soaked into 5min in 30% aqueous solution of nitric acid；By 1.5g nitric acid
Cobalt, 0.45g ammonium fluorides and 1.5g urea are dissolved in 50mL distilled water, be slowly stirred 30min and mixed liquor is made, then will mixing
Liquid is transferred in reactor, and adds the nickel foam of acid treatment obtained above；2h is reacted at 110 DEG C, it is cold after the completion of reaction
But to room temperature, the washing of obtained solid product is dried, Co is made in calcining 3h at 400 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer
Linear array is classified as negative electrode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from
Sub- liquid, obtains the Co for having silicon layer to surface3O4Nano wire, finally carries out surface spray C processing, dries, tabletting, negative plate is made；Its
In, the condition of constant pressure deposition is：The Co of the direct growth nickel foam prepared3O4Nano-wire array is made as negative electrode, Pt nets electrode
For inert anode, contain 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, when
Between be 2h；
(5) positive plate, barrier film, negative plate are sequentially overlapped, the volume heart are made, is sealed in battery container, inject electrolyte,
Preliminary filling, aging, chemical conversion, are made lithium ion battery.
Wherein, barrier film is that, by nano aluminium oxide and the mixing of micrometer alumina and pore creating material, secondary high-temperature sintering is obtained
Multiaperture pellumina, its thickness is 90 μm, and pore size is 200nm.
Embodiment 4
A kind of preparation method of new type lithium ion battery, comprises the following steps：
(1) nickel foam will be soaked as conductive current collector after 5min, by source of iron, phosphorus in 30% aqueous solution of nitric acid
Source, glucose are dissolved in water and mixed solution A are made, and add Quadrafos, be well mixed obtained mixed solution B, precipitating reagent is dissolved in
Precipitant solution is made in water, and nickel foam is added in reactor, then while respectively adding mixed solution B, precipitant solution
Enter into reactor, coprecipitation reaction 3-7h, obtained product washing obtains iron phosphorus presoma after drying；Wherein, Quadrafos
Addition be phosphorus source, the 7% of source of iron and glucose gross weight；The adding speed of mixed solution B and precipitant solution is respectively：
3 ls/h, 1.5 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, at 850 DEG C sinter
100min, tabletting, section obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam being soaked into 5min in 30% aqueous solution of nitric acid；By 2g cobalt nitrates,
0.4g ammonium fluorides and 2g urea are dissolved in 50mL distilled water, be slowly stirred 30min and mixed liquor is made, then shift mixed liquor
To reactor, and add the nickel foam of acid treatment obtained above；Reacted at 120 DEG C and be cooled to room after the completion of 3h, reaction
Temperature, obtained solid product washing is dried, Co is made in calcining 3h at 400 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer
Linear array is classified as negative electrode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from
Sub- liquid, obtains the Co for having silicon layer to surface3O4Nano wire, finally carries out surface spray C processing, dries, tabletting, negative plate is made；Its
In, the condition of constant pressure deposition is：The Co of the direct growth nickel foam prepared3O4Nano-wire array is made as negative electrode, Pt nets electrode
For inert anode, contain 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, when
Between be 4h；
(5) positive plate, barrier film, negative plate are sequentially overlapped, the volume heart are made, is sealed in battery container, inject electrolyte,
Preliminary filling, aging, chemical conversion, are made lithium ion battery.
Wherein, barrier film is that, by nano aluminium oxide and the mixing of micrometer alumina and pore creating material, secondary high-temperature sintering is obtained
Multiaperture pellumina, its thickness is 100 μm, and pore size is 200nm.
Embodiment 5
A kind of preparation method of new type lithium ion battery, comprises the following steps：
(1) nickel foam will be soaked as conductive current collector after 5min, by source of iron, phosphorus in 30% aqueous solution of nitric acid
Source, glucose are dissolved in water and mixed solution A are made, and add Quadrafos, be well mixed obtained mixed solution B, precipitating reagent is dissolved in
Precipitant solution is made in water, and nickel foam is added in reactor, then while respectively adding mixed solution B, precipitant solution
Enter into reactor, coprecipitation reaction 3-7h, obtained product washing obtains iron phosphorus presoma after drying；Wherein, Quadrafos
Addition be phosphorus source, the 8% of source of iron and glucose gross weight；The adding speed of mixed solution B and precipitant solution is respectively：
4.5 ls/h, 2 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, sinter 50min at 900 DEG C,
Tabletting, section obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam being soaked into 5min in 30% aqueous solution of nitric acid；By 2.5g nitric acid
Cobalt, 0.35g ammonium fluorides and 2.5g urea are dissolved in 50mL distilled water, be slowly stirred 30min and mixed liquor is made, then will mixing
Liquid is transferred in reactor, and adds the nickel foam of acid treatment obtained above；4.5h is reacted at 120 DEG C, after the completion of reaction
Room temperature is cooled to, the washing of obtained solid product is dried, Co is made in calcining 3h at 400 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer
Linear array is classified as negative electrode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from
Sub- liquid, obtains the Co for having silicon layer to surface3O4Nano wire, finally carries out surface spray C processing, dries, tabletting, negative plate is made；Its
In, the condition of constant pressure deposition is：The Co of the direct growth nickel foam prepared3O4Nano-wire array is made as negative electrode, Pt nets electrode
For inert anode, contain 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, when
Between be 4h；
(5) positive plate, barrier film, negative plate are sequentially overlapped, the volume heart are made, is sealed in battery container, inject electrolyte,
Preliminary filling, aging, chemical conversion, are made lithium ion battery.
Wherein, barrier film is that, by nano aluminium oxide and the mixing of micrometer alumina and pore creating material, secondary high-temperature sintering is obtained
Multiaperture pellumina, its thickness is 110 μm, and pore size is 200nm.
Comparative example 1
Quadrafos is added without in the preparation process of positive electrode, other conditions and embodiment 5 are identical.
Comparative example 2
Citric acid is added in the preparation process of positive electrode and substitutes Quadrafos, other conditions and embodiment 5 are identical.
Comparative example 3
Negative material is Co3O4Nano-wire array, its surface does not have silicon layer and carbon-coating, and other conditions and embodiment 5 are identical.
Performance test is carried out to lithium ion battery produced by the present invention below.
Electrochemical property test：
Normal temperature discharge and recharge is carried out to above-mentioned battery with 0.5C electric current, is circulated 500 times, the cyclicity of lithium ion battery is tested
Can, comprise the following steps that：(1) constant-current discharge：Electric current is 0.5C, and blanking voltage is 3V；(2) shelve：5 minutes；(3) constant current constant voltage
Charging：0.5C constant-current charges are to voltage 4.2V, then 4.2V constant-voltage charges, and cut-off current is 0.05C；(4) shelve：5 minutes；
(5) constant-current discharge：Electric current is 0.5C, and blanking voltage is 3V；(6) shelve：5 minutes；(7) cycle-index：500 times, opened from (3)
Begin；(8) terminate.For safety, it is 4.5V generally to set charging upper limit, and charging lower limit is 2.5V.
After tested, the first discharge specific capacity of lithium ion battery made from embodiment 1 to embodiment 5 is 203.5-
212.3mAh/g, after circulating 500 times, specific discharge capacity conservation rate is more than 98.9%.
The first discharge specific capacity of the lithium ion battery of comparative example 1 is 137.5mAh/g, after circulating 500 times, and discharge specific volume
It is 73.5% to measure conservation rate.
The first discharge specific capacity of the lithium ion battery of comparative example 2 is 185.9mAh/g, after circulating 500 times, and discharge specific volume
It is 81.9% to measure conservation rate.
The discharge capacity first of the lithium ion battery of comparative example 3 is 109.5mAh/g, after circulating 500 times, specific discharge capacity
Conservation rate is 60.5%.
Claims (10)
1. a kind of preparation method of new type lithium ion battery, it is characterised in that comprise the following steps：
(1) using nickel foam after low-kappa number as conductive current collector, source of iron, phosphorus source, glucose are dissolved in into water, and that mixing is made is molten
Liquid A, adds Quadrafos, is well mixed obtained mixed solution B, and precipitating reagent is dissolved in into water is made precipitant solution, by nickel foam
It is added in reactor, then while mixed solution B, precipitant solution are added in reactor respectively, coprecipitation reaction 3-
7h, obtained product washing obtains iron phosphorus presoma after drying；
(2) the uniform rear high temperature sintering tabletting of iron phosphorus presoma obtained above and lithium hydroxide mixed grinding, section are obtained
LiFePO4Positive plate；
(3) it regard nickel foam as conductive current collector after low-kappa number；By cobalt nitrate, urea and ammonium fluoride and the well mixed system of water
Mixed liquor is obtained, then mixed liquor is transferred in reactor, and add the nickel foam of acid treatment obtained above；Heating response,
Room temperature is cooled to after the completion of reaction, obtained solid product washing is dried, Co is made in high-temperature calcination3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer linear array
Negative electrode is classified as, inert electrode carries out constant pressure electro-deposition as anode, and electro-deposition product is cleaned by organic matter, removes ionic liquid
Body, obtains the Co for having silicon layer to surface3O4Nano wire, finally carries out surface spray C processing, dries, tabletting, negative plate is made；
(5) positive plate, barrier film, negative plate are sequentially overlapped, the volume heart is made, is sealed in battery container, inject electrolyte, in advance
Fill, aging, chemical conversion, be made lithium ion battery.
2. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：It is described in step (1)
The addition of Quadrafos is the 5-10% of phosphorus source, source of iron and glucose gross weight.
3. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：Low-kappa number nickel foam
Concrete operations be：Nickel foam is soaked into 5min in 30% aqueous solution of nitric acid.
4. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：In step (1), mixing
The adding speed of solution B and precipitant solution is respectively：1-5 ls/h, 0.8-2.6 ls/h.
5. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：It is described in step (3)
The preparation method of mixed liquor is specially：1-3g cobalt nitrates, 0.3-0.5g ammonium fluorides and 1-3g urea are dissolved in 50mL distilled water
In, it is slowly stirred 30min.
6. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：It is described in step (3)
The temperature of heating response is 110-130 DEG C, and the time of reaction is 1-5h.
7. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：It is described in step (3)
The condition of high-temperature calcination is：1-4h is calcined at 350-450 DEG C.
8. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：It is described in step (4)
Constant pressure deposition condition be：The Co of the direct growth nickel foam prepared3O4Nano-wire array is used as negative electrode, Pt net electrode conducts
Inert anode, contains 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, the time
For 1-5h.
9. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：It is described in step (5)
Barrier film is the multiaperture pellumina made from secondary high-temperature sintering by nano aluminium oxide and the mixing of micrometer alumina and pore creating material,
Its thickness is 80-120 μm, and pore size is 100-300nm.
10. a kind of preparation method of new type lithium ion battery as claimed in claim 1, it is characterised in that：In step (2), institute
The temperature for stating high temperature sintering is 720-960 DEG C, and the time is 30-120min.
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