CN110137445A - Battery anode slice, lithium ion battery, stratiform nickel ion doped and preparation method thereof - Google Patents
Battery anode slice, lithium ion battery, stratiform nickel ion doped and preparation method thereof Download PDFInfo
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- CN110137445A CN110137445A CN201910233977.0A CN201910233977A CN110137445A CN 110137445 A CN110137445 A CN 110137445A CN 201910233977 A CN201910233977 A CN 201910233977A CN 110137445 A CN110137445 A CN 110137445A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000007774 positive electrode material Substances 0.000 claims abstract description 33
- 239000006258 conductive agent Substances 0.000 claims abstract description 26
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229910013713 LiNixMnyO2 Inorganic materials 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 38
- 239000012266 salt solution Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000013067 intermediate product Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000011343 solid material Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000375 suspending agent Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 239000002002 slurry Substances 0.000 description 40
- 239000000047 product Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 238000005096 rolling process Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- -1 polypropylene Polymers 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000005030 aluminium foil Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NOMICGATVHRDNY-UHFFFAOYSA-N [Mn].Cl(=O)(=O)O Chemical compound [Mn].Cl(=O)(=O)O NOMICGATVHRDNY-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KXXCZYZSRRVYST-UHFFFAOYSA-N chloric acid;nickel Chemical compound [Ni].OCl(=O)=O KXXCZYZSRRVYST-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000009466 transformation Effects 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
- H01M10/052—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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention is suitable for field of lithium ion battery, disclose battery anode slice, lithium ion battery, the preparation method of stratiform nickel ion doped and stratiform nickel ion doped, wherein, battery anode slice includes cathode metal substrate and coated on the positive coating outside the cathode metal substrate, the component of the anode coating includes positive active material, positive electrode binder, positive conductive agent, and the positive active material is stratiform nickel ion doped LiNixMnyO2, wherein x=0.6~0.8, y=1-x.The present invention uses stratiform nickel ion doped LiNixMnyO2(wherein x=0.6~0.8, y=1-x) as a positive electrode active material, improves the thermal stability and processing performance of positive active material, reduces the cost of battery anode slice.Using lithium ion battery made of battery anode slice of the invention, have the advantages that at low cost, specific energy is high, stability of material is high, have a safety feature, good cycle, cost performance it is high.
Description
Technical field
The present invention relates to field of lithium ion battery more particularly to a kind of battery anode slice, with the lithium of the battery anode slice
The preparation method of ion battery, the stratiform nickel ion doped for being used to prepare the battery anode slice and stratiform nickel ion doped.
Background technique
With the development of mobile electronic device, the demand of battery is increasing, to the capacity, voltage, service life of battery
And use cost made higher requirement.Lithium ion battery is a kind of secondary cell (rechargeable battery), it is relied primarily on
The movement of lithium ion between a positive electrode and a negative electrode carrys out work.
However, lithium ion battery in the prior art uses ternary material nickle cobalt lithium manganate as a positive electrode active material, lead
Cause that the generally existing battery roll core poor safety performance of existing lithium ion battery, capacity is low, power is low, the defect of poor circulation.
In addition, contain high-cost rare element cobalt in ternary material nickle cobalt lithium manganate, poor processability, and to the wet of production environment
Degree requires height, slurry retrogradation after water suction easily occurs, causes coated face density unstable, consequently lead to the production of a variety of bad problems
It is raw, such as: the product qualification rate of production is lower than 90%；The poor safety performance of product, needle are pierced essentially by not；The heat of battery is steady
Qualitative difference is easy thermal diffusion after internal short-circuit of battery, causes on fire from explosion；Cycle performance 0.5C/1C charge and discharge is lower than 500 weeks；Weight
It is low to measure specific energy；Volumetric power density is low.
Summary of the invention
The first purpose of this invention is to provide a kind of battery anode slice, aims to solve the problem that existing battery anode slice uses
To there is at high cost, poor processability, stability in ternary material nickle cobalt lithium manganate poor, poor circulation as a positive electrode active material
Technical problem.
In order to achieve the above objectives, scheme provided by the invention is: battery anode slice, including cathode metal substrate and is coated on
The component of positive coating outside the cathode metal substrate, the anode coating includes positive active material, positive electrode binder, just
Pole conductive agent, the positive active material are stratiform nickel ion doped LiNixMnyO2, wherein x=0.6~0.8, y=1-x.
Optionally, the positive coating includes the component of following parts by weight:
Positive active material 98.34%~99.28%；
Positive conductive agent 0.02%~0.06%；
Positive electrode binder 0.7%~1.6%.
Optionally, the positive coating includes the component of following parts by weight: positive active material 98.87%；Anode is led
Electric agent 0.03%；Positive electrode binder 1.1%；Alternatively,
The anode coating includes the component of following parts by weight: positive active material 98.75%；Positive conductive agent
0.05%；Positive electrode binder 1.2%；Alternatively,
The anode coating includes the component of following parts by weight: positive active material 98.76%；Positive conductive agent
0.04%；Positive electrode binder 1.2%；Alternatively,
The anode coating includes the component of following parts by weight: positive active material 98.8%；Positive conductive agent
0.05%；Positive electrode binder 1.15%.
Optionally, the positive conductive agent include electrically conductive graphite, conductive carbon black, carbon fiber, carbon nanotube, in graphene
It is at least one；And/or
The positive electrode binder is polyvinylidene fluoride.
Second object of the present invention is to provide a kind of lithium ion battery comprising battery case, battery cathode sheet,
One diaphragm, the second diaphragm, electrolyte and above-mentioned battery anode slice, the battery anode slice, the battery cathode sheet, described
One diaphragm, second diaphragm and the electrolyte are all set in the battery case, and the battery anode slice, the battery
Negative electrode tab, first diaphragm, second diaphragm are all dipped in the electrolyte, and the battery cathode sheet is located at the battery
Between positive plate and the battery case, first diaphragm is set between the battery anode slice and the battery cathode sheet,
Second diaphragm is set between the battery case and the battery cathode sheet.
Optionally, the battery cathode sheet includes negative metal substrate and coated on the cathode outside the negative metal substrate
Coating, the cathode coating include following component in parts by weight:
Negative electrode active material 96.4%~98.2%；
Cathode conductive agent 0%-1%；
Suspending agent 0.8%~1.3%；
Negative electrode binder 1%~1.3%.
Third object of the present invention is to provide a kind of preparation method of stratiform nickel ion doped comprising following steps:
Nickel salt solution and manganese salt solution are mixed, metal salt solution is made；
The metal salt solution and enveloping agent solution, precipitant solution are subjected to precipitation reaction, solid-liquid mixed liquor is made；
The solid-liquid mixed liquor is separated by solid-liquid separation, solid spherical nickel-manganese binary presoma is obtained；
By the spherical nickel-manganese binary presoma and lithium source mixed sintering, broken, obtained sintering intermediate products；
It after the sintering intermediate products are carried out alumina-coated processing, then is sintered, is crushed, stratiform nickel mangaic acid is made
Lithium LiNixMnyO2, wherein x=0.6~0.8, y=1-x.
Optionally, the nickel salt solution and manganese salt solution be blended in the first container made of plating Teflon material into
Row.
Optionally, the precipitation reaction of the metal salt solution and enveloping agent solution, the precipitant solution is being equipped with bottom liquid
It is carried out in the second container of protective gas, the bottom liquid is water, in ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide
Any one or any combination, and the pH value of the bottom liquid is 10~12, the protective gas is inert gas；And/or
The precipitation reaction embodiment of the metal salt solution and enveloping agent solution, the precipitant solution are as follows: will be described
Metal salt solution cocurrent together with the enveloping agent solution, the precipitant solution, which is added in second container, carries out precipitation reaction,
Continue heating, stirring after charging so that the metal salt solution and the enveloping agent solution, the precipitant solution after
Continuous rest on carries out precipitation reaction in the second container；And/or
The embodiment that the solid-liquid mixed liquor is separated by solid-liquid separation are as follows: the solid-liquid mixed liquor is subjected to solid-liquid point
From solid material obtained after separation is aged, the solid material after ageing is separated by solid-liquid separation again, is obtained described
Spherical nickel-manganese binary presoma；And/or
The enveloping agent solution is ammonia spirit, and the precipitant solution is sodium hydroxide solution.
Fourth object of the present invention is to provide a kind of stratiform nickel ion doped, uses above-mentioned stratiform nickel ion doped
Preparation method is made.
The beneficial effects of the present invention are:
Battery anode slice of the invention is due to using stratiform nickel ion doped LiNixMnyO2(wherein x=0.6~0.8, y=1-
X) as a positive electrode active material, therefore, stratiform nickel ion doped LiNi can on the one hand be utilizedxMnyO2Structural stability is good, processing performance
Preferred characteristic improves the thermal stability and processing performance of positive active material, reduces the humidity requirement to production environment；
On the other hand the use of the rare element cobalt of high cost is avoided, to reduce the cost of battery anode slice, cost advantage is aobvious
It writes；Another further aspect is high using specific energy within 4.5V, good cycle.
Using lithium ion battery made of battery anode slice of the invention, at low cost, specific energy is high, stability of material
The high advantage of height, good cycle, cost performance, and battery anode slice is not hygroscopic in wet condition, does not easily cause lithium ion
Internal short-circuit of battery makes lithium ion battery provided by the present invention have the advantages that long service life, using safe.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
It is to be appreciated that in the embodiment of the present invention, when an element is referred to as being " fixed " or " disposed " on another element,
It directly on the other element or can may be simultaneously present centering elements.When an element be known as " connection " it is another
A element, it, which can be, is directly connected to another element or may be simultaneously present centering elements.
In addition, the description for being related to " first ", " second " etc. in the present invention is used for description purposes only, and should not be understood as referring to
Show or imply its relative importance or implicitly indicates the quantity of indicated technical characteristic." first ", " are defined as a result,
Two " feature can explicitly or implicitly include at least one of the features.In addition, the technical solution between each embodiment can
It to be combined with each other, but must be based on can be realized by those of ordinary skill in the art, when the combination of technical solution occurs
Conflicting or cannot achieve when, will be understood that the combination of this technical solution is not present, also not the present invention claims protection model
Within enclosing.
Battery anode slice provided in an embodiment of the present invention, including cathode metal substrate and be coated on the cathode metal substrate
The component of outer positive coating, the anode coating includes positive active material, positive electrode binder, positive conductive agent, it is described just
Pole active material is stratiform nickel ion doped LiNixMnyO2, wherein x=0.6~0.8, y=1-x.The battery of the embodiment of the present invention is just
Pole piece is due to using stratiform nickel ion doped LiNixMnyO2(wherein x=0.6~0.8, y=1-x) as a positive electrode active material, therefore,
On the one hand stratiform nickel ion doped LiNi can be utilizedxMnyO2Structural stability is good, the preferred characteristic of processing performance, improves positive work
Property substance thermal stability and processing performance, reduce to the requirement of the humidity of production environment；On the other hand it is dilute to avoid high cost
The use of element cobalt is lacked, to reduce the cost of battery anode slice, cost advantage is significant；Another further aspect makes within 4.5V
With specific energy height, good cycle.
Preferably, the positive coating includes the component of following parts by weight:
Positive active material 98.34%~99.28%；
Positive conductive agent 0.02%~0.06%；
Positive electrode binder 0.7%~1.6%.
Herein, it is optimized by the component proportion to positive coating, conducive to the comprehensive of battery anode slice is improved
Can, to be conducive to improve structural stability, long circulation life and the security reliability of lithium ion battery.
Preferably, the positive conductive agent include electrically conductive graphite, conductive carbon black, carbon fiber, carbon nanotube, in graphene
It is at least one.As a preferred embodiment of the present embodiment, the positive conductive agent is greater than 20 μ using diameter 1-5nm, length
The single-walled carbon nanotube of m can effectively promote the use ratio of positive electrode active material material in this way.
Preferably, the positive electrode binder is polyvinylidene fluoride.
Positive electrode binder uses polyvinylidene fluoride, in this way, by may make positive conductive agent, positive electrode binder and stratiform
Nickel ion doped LiNixMnyO2In conjunction with positive coating stability obtained, more preferable, cycle performance more preferably, is conducive to improving performance battery just
The comprehensive performance of pole piece.
Preferably, cathode metal substrate is aluminium foil, can meet the electric conductivity requirement of battery anode slice, and quality
Gently, at low cost.It of courses, in concrete application, the material of cathode metal substrate is without being limited thereto.
The preparation method of stratiform nickel ion doped provided in an embodiment of the present invention comprising following steps:
Nickel salt solution and manganese salt solution are mixed, are made metal salt solution, nickel salt solution concretely nickel sulfate solution, nitre
Sour nickel solution, chloric acid nickel solution etc., manganese salt solution concretely manganese sulfate solution, manganese nitrate solution, chloric acid manganese solution etc.；
The metal salt solution and enveloping agent solution, precipitant solution are subjected to precipitation reaction, solid-liquid mixed liquor is made；
The solid-liquid mixed liquor is separated by solid-liquid separation, solid spherical nickel-manganese binary presoma is obtained；
By the spherical nickel-manganese binary presoma and lithium source mixed sintering, broken, obtained sintering intermediate products；
It after the sintering intermediate products are carried out alumina-coated processing, then is sintered, is crushed, stratiform nickel mangaic acid is made
Lithium LiNixMnyO2, wherein x=0.6~0.8, y=1-x.Herein, it is produced among treated the sintering of aluminium cladding will be changed
It can again include also sieving screening, in this way, the partial size that stratiform nickel ion doped can be obtained is more balanced after product are sintered, are broken.
Using the preparation method of stratiform nickel ion doped provided in an embodiment of the present invention, manufactured stratiform nickel ion doped
LiNixMnyO2Material structure stability is good, and processing performance is superior, and specific energy height is used within 4.5V and cost advantage is significant,
And the lithium ion battery of its production has the advantages that security performance is high, specific energy is high, cost of material is low (cost performance is high).
Preferably, the nickel salt solution and manganese salt solution be blended in the first container made of plating Teflon material into
Row, in this way, being conducive to prevent the first container from chemically reacting with nickel salt solution, manganese salt solution.The first container is preferably tank body.
Preferably, the precipitation reaction of the metal salt solution and enveloping agent solution, the precipitant solution is being equipped with bottom liquid
It is carried out in the second container of protective gas, the bottom liquid is water, in ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide
Any one or any combination, and the pH value of the bottom liquid is 10~12.The protective gas is inert gas, such as nitrogen, argon
Gas etc..The setting of protective gas, conducive to preventing that oxidation reaction occurs during precipitation reaction.By the setting of the pH value of bottom liquid 10~
12, conducive to acid-base integration reaction is prevented, and it is conducive to accelerate the progress of precipitation reaction.Second container is preferably reaction kettle.
Preferably, the precipitation reaction embodiment of the metal salt solution and enveloping agent solution, the precipitant solution are as follows:
The metal salt solution is precipitated in cocurrent addition second container together with the enveloping agent solution, the precipitant solution
Reaction continues heating, stirring after charging, so that the metal salt solution and the enveloping agent solution, the precipitating reagent
Solution, which remains in, carries out precipitation reaction in the second container.During precipitation reaction, solid material can constantly be precipitated.
Preferably, the embodiment solid-liquid mixed liquor being separated by solid-liquid separation are as follows: carry out the solid-liquid mixed liquor
It is separated by solid-liquid separation, solid material obtained after separation is aged, the solid material after ageing is separated by solid-liquid separation again, is obtained
To the spherical nickel-manganese binary presoma.Herein, solid-liquid mixed liquor is separated by solid-liquid separation twice, conducive to relatively dry ball is obtained
Shape nickel manganese binary presoma.
Preferably, the enveloping agent solution is ammonia spirit, and the precipitant solution is sodium hydroxide solution.
Preferably, the battery anode slice is prepared with the following method:
(1) each component of positive coating and solvent NMP (N-Methyl pyrrolidone) are added in double-planet beater jointly,
2h is stirred under conditions of rotational velocity is 48r/min, revolution speed is 1700r/min, and slurry is made；
(2) use high speed disperser under conditions of revolving speed is 3500~4500r/min, the slurry that dispersion steps (1) obtain
Material, until viscosity reaches 5000~8000mPas；
(3) step (2) obtained slurry is coated on the aluminium foil of 12~16 μ m-thicks according to the surface density of 200~230g/ ㎡,
Positive plate intermediate product is made in drying, dries manufactured positive plate intermediate product preferred water content and is less than or equal to 0.15%；
(4) by positive plate intermediate product according to 3.4~3.6g/mm of positive active material3Compacted density carry out rolling system
Product is compacted at closely knit positive plate；
(5) positive plate compacting product is cut to the battery anode slice that width is required for technique.
Lithium ion battery provided in an embodiment of the present invention, including battery case, battery cathode sheet, the first diaphragm, second every
Film, electrolyte and above-mentioned battery anode slice, the battery anode slice, the battery cathode sheet, first diaphragm, described
Two diaphragms and the electrolyte are all set in the battery case, and the battery anode slice, the battery cathode sheet, described
One diaphragm, second diaphragm are all dipped in the electrolyte, the battery cathode sheet be located at the battery anode slice with it is described
Between battery case, first diaphragm is set between the battery anode slice and the battery cathode sheet, second diaphragm
Between the battery case and the battery cathode sheet.Lithium ion battery provided in an embodiment of the present invention, due to using
Above-mentioned battery anode slice, therefore, with that at low cost, specific energy is high, stability of material is high, good cycle, cost performance are high is excellent
Point, and it is not hygroscopic in wet condition, it does not easily cause inside lithium ion cell short-circuit, makes lithium provided by the embodiment of the present invention
Ion battery has the advantages that long service life, using safe.
Preferably, the battery cathode sheet includes negative metal substrate and coated on the cathode outside the negative metal substrate
Coating, the cathode coating include following component in parts by weight:
Negative electrode active material 96.4%~98.2%；
Cathode conductive agent 0%-1%；
Suspending agent 0.8%~1.3%；
Negative electrode binder 1%~1.3%.
Preferably, negative electrode active material is graphite.
Preferably, cathode conductive agent includes at least one of conductive carbon black, electrically conductive graphite, carbon nanotube.Herein, pass through
The material of cathode conductive agent is optimized, conducive to the internal resistance for reducing battery.
Preferably, negative electrode binder include sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR), polyacrylic acid (PAA),
At least one of sodium alginate.Herein, it is optimized by the material to negative electrode binder, is conducive to guarantee cathode coating
There is good adhesive property with negative metal substrate.
Preferably, suspending agent is sodium carboxymethylcellulose (CMC).Herein, suspending agent uses sodium carboxymethylcellulose, in addition to
Cathode conductive agent, negative electrode active material can be made to be in outside suspended state in the negative electrode slurry made, meanwhile, using carboxymethyl
The cementitiousness of sodium cellulosate acts synergistically with negative electrode binder, and cathode coating each group divides it after improving battery cathode sheet drying
Between and the adhesive force between cathode coating and negative metal substrate.
As a preferred embodiment of the present embodiment, negative electrode active material uses gram volume for the day of 360mAh/g or more
Right graphite, natural graphite cost performance are high.Cathode conductive agent uses conductive carbon black.Suspending agent is using high molecular weight, high substituted degree
Sodium carboxymethylcellulose.Negative electrode binder uses short grained butadiene-styrene rubber, can effectively improve making for negative electrode active material in this way
Use ratio.
Preferably, first diaphragm and the second diaphragm are all high intensity, high-modulus, 9-14 μm of thickness of film.
Preferably, the first diaphragm, second diaphragm all use MODIFIED PP/PE plastics of high molecular weight, i.e. the first diaphragm,
Second diaphragm all uses PP (polypropylene) and PE (polyethylene) to be mixed, and tensile strength and modulus are high.
Preferably, the battery cathode sheet is prepared by the following method:
(1) each component of cathode coating and solvent deionized water are added to jointly in double-planet beater, from revolving speed
Slurry is made in stirring 2h under conditions of degree is 48r/min, revolution speed is 1500r/min；
(2) use high speed disperser under conditions of revolving speed is 3000~4000r/min, dispersion steps (1) obtained slurry,
Reach 3000~6000mPas to slurry viscosity；
(3) slurry is coated on the copper foil of 8~10 μ m-thicks according to the surface density of 100~120g/ ㎡, cathode is made in drying
Piece intermediate product dries manufactured negative electrode tab intermediate product preferred water content and is less than or equal to 0.15%；
(4) by negative electrode tab intermediate product according to 1.5~1.7g/mm of negative electrode active material3Compacted density carry out rolling system
Product is compacted at closely knit negative electrode tab；
(5) negative electrode tab compacting product is cut to the battery cathode sheet that width is required for technique.
Preferably, the preparation method for the lithium ion battery that the embodiment of the present invention also provides, includes the following steps:
(1) battery anode slice, battery cathode sheet are mounted on automatic winding-machine as requested respectively, using diaphragm every
Aluminium strip anode ear is welded from battery anode slice and battery cathode sheet, while to battery anode slice, it is negative that battery cathode sheet welds nickel strap
It is wound after tab, core is made；The diaphragm is preferably high intensity, high-modulus, 9-14 μm of thickness of film；
(2) core is inserted into jig, vacuum oven is put into, by being evacuated to -85~-95MPa, at 75~95 DEG C
Constant temperature and pressure baking, nitrogen charging to air pressure is -35~-45MPa later；It vacuumizes, toast, inflated with nitrogen circulation implementation 8~14 hours,
Water content≤300PPM into core；
(3) core is installed into steel shell, welds negative electrode lug and steel shell, Upper gasket, slot rolling, test short circuit, injection are installed
5.5~5.9g electrolyte welds anode ear and nut cap, then nut cap and steel shell is fastened sealing and form battery core；Clean battery core appearance
Face；Operations in this step are preferably 20-25 DEG C, complete in -38--45 DEG C of dew point of environment in environment temperature；
(4) battery core is placed on after being activated 24~48 hours in the environment of temperature is 30~40 DEG C, is installed on formation cabinet
Carrying out chemical conversion upper limit voltage is 4.35V；Aging five days in the environment of battery core is firstly placed on 25~35 DEG C of temperature, then to battery core into
Row voltage internal resistance screening screens battery core partial volume list charging voltage in the battery core of 3.6~3.9V, then is placed on aging five in the environment of room temperature
It, is made finished product lithium ion battery.
The preparation of different battery anode slices, battery cathode sheet, lithium ion battery is described in detail respectively below by way of specific embodiment
The preferred embodiment of method.
Embodiment 1:
Battery anode slice provided in this embodiment, positive coating include following component according to parts by weight:
Stratiform nickel ion doped LiNi0.65Mn0.35O298.87%；
Carbon nanotube 0.03%；
Polyvinylidene fluoride 1.1%.
The battery anode slice is prepared by the following method:
(1.1) by above-mentioned each component (stratiform nickel ion doped LiNi0.65Mn0.35O2, carbon nanotube, polyvinylidene fluoride) press
Ratio and solvent NMP (N-Methyl pyrrolidone) are added in double-planet beater jointly, are 48r/min, revolve in rotational velocity
Slurry is made in stirring 2h under conditions of speed is 1700r/min；
(1.2) the high speed disperser slurry that dispersion steps (1.1) obtain under conditions of revolving speed is 3500r/min is used,
Until the viscosity of slurry reaches 5000mPas；
(1.3) step (1.2) slurry obtained is coated on the aluminium foil of 14 μ m-thicks according to the surface density of 225g/ ㎡ and is obtained
To positive plate blank, positive plate blank is dried to water content less than or equal to 0.15%, positive plate intermediate product is made；
(1.4) by positive plate intermediate product according to positive active material 3.5g/mm3Compacted density carry out rolling be made it is close
Real positive plate is compacted product；
(1.5) positive plate compacting product is cut into the battery anode slice for 57mm wide.
Embodiment 2:
Battery anode slice provided in this embodiment, positive coating include following component according to parts by weight:
Stratiform nickel ion doped LiNi0.75Mn0.25O298.75%；
Carbon nanotube 0.05%；
Polyvinylidene fluoride 1.2%.
The battery anode slice is prepared by the following method:
(2.1) by above-mentioned each component (stratiform nickel ion doped LiNi0.75Mn0.25O2, carbon nanotube, polyvinylidene fluoride) press
Ratio and solvent NMP (N-Methyl pyrrolidone) are added in double-planet beater jointly, are 48r/min, revolve in rotational velocity
Slurry is made in stirring 2h under conditions of speed is 1700r/min；
(2.2) the high speed disperser slurry that dispersion steps (2.1) obtain under conditions of revolving speed is 4500r/min is used,
Until the viscosity of slurry reaches 6000mPas；
(2.3) step (2.2) slurry obtained is coated on the aluminium foil of 12 μ m-thicks according to the surface density of 220g/ ㎡ and is obtained
To positive plate blank, positive plate blank is dried to water content less than or equal to 0.15%, positive plate intermediate product is made；
(2.4) by positive plate intermediate product according to positive active material 3.55g/mm3Compacted density carry out rolling be made
Closely knit positive plate is compacted product；
(2.5) positive plate compacting product is cut into the battery anode slice for 58mm wide.
Embodiment 3:
Battery anode slice provided in this embodiment, positive coating include following component according to parts by weight:
Stratiform nickel ion doped LiNi0.65Mn0.35O298.76%；
Carbon nanotube 0.04%；
Polyvinylidene fluoride 1.2%.
The battery anode slice is prepared by the following method:
(3.1) by above-mentioned each component (stratiform nickel ion doped LiNi0.65Mn0.35O2, carbon nanotube, polyvinylidene fluoride) press
Ratio and solvent NMP (N-Methyl pyrrolidone) are added in double-planet beater, are 48r/min, revolution speed in rotational velocity
Slurry is made to stir 2h under conditions of 1700r/min；
(3.2) the high speed disperser slurry that dispersion steps (3.1) obtain under conditions of revolving speed is 4000r/min is used,
Until the viscosity of slurry reaches 6000mPas；
(3.3) step (3.2) slurry obtained is coated on the aluminium foil of 14 μ m-thicks according to the surface density of 215g/ ㎡ and is obtained
To positive plate blank, positive plate blank is dried to water content less than or equal to 0.15%, positive plate intermediate product is made；
(3.4) by positive plate intermediate product according to positive active material 3.45g/mm3Compacted density carry out rolling be made
Closely knit positive plate is compacted product；
(3.5) positive plate compacting product is cut into the battery anode slice for 57.5mm wide.
Embodiment 4:
Battery anode slice provided in this embodiment, positive coating include following component according to parts by weight:
Stratiform nickel ion doped LiNi0.68Mn0.32O298.8%；
Carbon nanotube 0.05%；
Polyvinylidene fluoride 1.15%.
The battery anode slice is prepared by the following method:
(4.1) by above-mentioned each component (stratiform nickel ion doped LiNi0.75Mn0.25O2, carbon nanotube, polyvinylidene fluoride) press
Ratio and solvent NMP (N-Methyl pyrrolidone) are added in double-planet beater jointly, are 48r/min, revolve in rotational velocity
Slurry is made in stirring 2h under conditions of speed is 1700r/min；
(4.2) the high speed disperser slurry that dispersion steps (4.1) obtain under conditions of revolving speed is 4500r/min is used,
Until the viscosity of slurry reaches 6000mPas；
(4.3) step (4.2) slurry obtained is coated on the aluminium foil of 12 μ m-thicks according to the surface density of 200g/ ㎡ and is obtained
To positive plate blank, positive plate blank is dried to water content less than or equal to 0.15%, positive plate intermediate product is made；
(4.4) by positive plate intermediate product according to positive active material 3.5g/mm3Compacted density carry out rolling be made it is close
Real positive plate is compacted product；
(4.5) positive plate compacting product is cut into the battery anode slice for 58mm wide.
Embodiment 5:
Battery cathode sheet provided in this embodiment, cathode coating include following component according to parts by weight:
The gram volume of the graphite is 360mAh/g.
The battery cathode sheet is prepared by the following method:
(5.1) above-mentioned each component (graphite, conductive black, sodium carboxymethylcellulose, butadiene-styrene rubber) is proportionally and molten
Agent deionized water is added to jointly in double-planet beater, rotational velocity is 48r/min, revolution speed is 1500r/min's
Under the conditions of stirring 2h slurry is made；
(5.2) use high speed disperser under conditions of revolving speed is 3000r/min, dispersion steps (5.1) slurry obtained
Material, until the viscosity of slurry reaches 5000mPas；
(5.3) step (5.2) slurry obtained is coated on the copper foil of 9 μ m-thicks according to the surface density of 118g/ ㎡ and is made
Negative electrode tab blank is obtained, negative electrode tab blank water content is dried to less than or equal to 0.15%, negative electrode tab intermediate product is made；
(5.4) by negative electrode tab intermediate product according to negative electrode active material 1.65g/mm3Compacted density carry out rolling be made
Closely knit negative electrode tab is compacted product；
(5.5) negative electrode tab compacting product is cut into the battery cathode sheet for 59mm wide.
Embodiment 6:
Battery cathode sheet provided in this embodiment, cathode coating include following component according to parts by weight:
The gram volume of the graphite is 360mAh/g.
The battery cathode sheet is prepared by the following method:
(6.1) above-mentioned each component (graphite, conductive black, sodium carboxymethylcellulose, butadiene-styrene rubber) is proportionally and molten
Agent deionized water is added to jointly in double-planet beater, rotational velocity is 48r/min, revolution speed is 1500r/min's
Under the conditions of stirring 2h slurry is made；
(6.2) use high speed disperser under conditions of revolving speed is 3500r/min, dispersion steps (6.1) slurry obtained
Material, until the viscosity of slurry reaches 4200mPas；
(6.3) step (6.2) slurry obtained is coated on the copper foil of 8 μ m-thicks according to the surface density of 114g/ ㎡ and is made
Negative electrode tab blank is obtained, negative electrode tab blank water content is dried to less than or equal to 0.15%, negative electrode tab intermediate product is made；
(6.4) by negative electrode tab intermediate product according to negative electrode active material 1.6g/mm3Compacted density carry out rolling be made it is close
Real negative electrode tab is compacted product；
(6.5) negative electrode tab compacting product is cut into the battery cathode sheet for 59.5mm wide.
Embodiment 7:
Battery cathode sheet provided in this embodiment, cathode coating include following component according to parts by weight:
The gram volume of the graphite is 360mAh/g.
The battery cathode sheet is prepared by the following method:
(7.1) above-mentioned each component (graphite, conductive black, sodium carboxymethylcellulose, butadiene-styrene rubber) is proportionally and molten
Agent deionized water is added to jointly in double-planet beater, rotational velocity is 48r/min, revolution speed is 1500r/min's
Under the conditions of stirring 2h slurry is made；
(7.2) use high speed disperser under conditions of revolving speed is 3800r/min, dispersion steps (7.1) slurry obtained
Material, until the viscosity of slurry reaches 5500mPas；
(7.3) step (7.2) slurry obtained is coated on the copper foil of 8 μ m-thicks according to the surface density of 110g/ ㎡ and is made
Negative electrode tab blank is obtained, negative electrode tab blank water content is dried to less than or equal to 0.15%, negative electrode tab intermediate product is made；
(7.4) by negative electrode tab intermediate product according to negative electrode active material 1.62g/mm3Compacted density carry out rolling be made
Closely knit negative electrode tab is compacted product；
(7.5) negative electrode tab compacting product is cut into the battery cathode sheet for 59mm wide.
Embodiment 8:
Battery cathode sheet provided in this embodiment, cathode coating include following component according to parts by weight:
The gram volume of the graphite is 360mAh/g.
The battery cathode sheet is prepared by the following method:
(8.1) above-mentioned each component (graphite, conductive black, sodium carboxymethylcellulose, butadiene-styrene rubber) is proportionally and molten
Agent deionized water is added to jointly in double-planet beater, rotational velocity is 40r/min, revolution speed is 1200r/min's
Under the conditions of stirring 1h slurry is made；
(8.2) use high speed disperser under conditions of revolving speed is 3000r/min, dispersion steps (8.1) slurry obtained
Material, the viscosity for being dispersed to slurry reach 4500mPas；
(8.3) step (8.2) slurry obtained is coated on the copper foil of 9 μ m-thicks according to the surface density of 100g/ ㎡ and is made
Negative electrode tab blank is obtained, negative electrode tab blank water content is dried to less than or equal to 0.15%, negative electrode tab intermediate product is made；
(8.4) by negative electrode tab intermediate product according to negative electrode active material 1.55g/mm3Compacted density carry out rolling be made
Closely knit negative electrode tab is compacted product；
(8.5) negative electrode tab compacting product is cut into the battery cathode sheet for 58.5mm wide.
Embodiment 9:
The preparation method of lithium ion battery provided in this embodiment, includes the following steps:
(9.1) battery anode slice, battery cathode sheet are mounted on automatic winding-machine as requested respectively, using diaphragm
Battery anode slice and battery cathode sheet is isolated, while aluminium strip anode ear is welded to battery anode slice, battery cathode sheet welds nickel strap
It is wound after negative electrode lug, core is made, the diaphragm is prepared by PP (polypropylene)/PE (polyethylene) substrate, i.e. diaphragm
It is mixed by PP (polypropylene) and PE (polyethylene)；
(9.2) core is inserted into jig, is put into vacuum oven, it is permanent in 85 DEG C of constant temperature by being evacuated to -90MPa
Pressure baking, nitrogen charging to air pressure is -40MPa later；It vacuumizes, toast, inflated with nitrogen circulation implementation 10 hours, until moisture content contains in core
Amount≤200PPM；
(9.3) core is installed into steel shell, welds negative electrode lug and steel shell, Upper gasket, slot rolling, test short circuit, note are installed
Enter 5.5g electrolyte, welds anode ear and nut cap, then nut cap and steel shell are fastened into sealing and form battery core (battery roll core)；Cleaning electricity
The outer surface of core；Operations are 23 DEG C, complete in -38 DEG C~-42 DEG C of dew point of environment in environment temperature in this step.
(9.4) battery core is placed on after being activated 35 hours in the environment of temperature is 30 DEG C, is installed on formation cabinet and is changed
At being charged to 4.35V；Then aging five days in the environment of battery core is firstly placed on 35 DEG C of temperature carries out voltage internal resistance sieve to battery core
Choosing, screening battery core partial volume list charging voltage then aging five days in the environment of being placed on 30 DEG C of temperature, are made in the battery core of 3.6V~3.9V
Lithium ion battery.
Embodiment 10:
The preparation method of lithium ion battery provided in this embodiment, includes the following steps:
(10.1) battery anode slice, battery cathode sheet are mounted on automatic winding-machine as requested respectively, using every
Battery anode slice and battery cathode sheet is isolated in film, while welding aluminium strip anode ear to battery anode slice, and battery cathode sheet welds nickel
It is wound after band negative electrode lug, core is made；The diaphragm is prepared by macromolecule PE (polyethylene) material；
(10.2) core is inserted into jig, is put into vacuum oven, it is permanent in 75 DEG C of constant temperature by being evacuated to -85MPa
Pressure baking, nitrogen charging to air pressure is -35MPa later；It vacuumizes, toast, inflated with nitrogen circulation implementation 14 hours, until moisture content contains in core
Amount≤200PPM；
(10.3) core is installed into steel shell, welds negative electrode lug and steel shell, Upper gasket, slot rolling, test short circuit, note are installed
Enter 5.7g electrolyte, welds anode ear and nut cap, then nut cap and steel shell are fastened into sealing and form battery core；Clean the appearance of battery core
Face；Operations are 20 DEG C, complete in the environment of Lu Dian≤- 40 DEG C~-43 DEG C in environment temperature in this step.
(10.4) battery core is placed on after being activated 30 hours in the environment of temperature is 35 DEG C, is installed on formation cabinet and is changed
At being charged to 4.4V；Then aging five days in the environment of battery core is firstly placed on 30 DEG C of temperature carries out voltage internal resistance screening to battery core,
Battery core partial volume list charging voltage is screened in the battery core of 3.6~3.9V, then aging five days in the environment of being placed on 25 DEG C of temperature, be made lithium from
Sub- battery.
Embodiment 11:
The preparation method of lithium ion battery provided in this embodiment, includes the following steps:
(11.1) battery anode slice, battery cathode sheet are mounted on automatic winding-machine as requested respectively, using every
Battery anode slice and battery cathode sheet is isolated in film, while welding aluminium strip anode ear to battery anode slice, and battery cathode sheet welds nickel
It is wound after band negative electrode lug, core is made；The diaphragm is prepared by PP；
(11.2) core is inserted into jig, is put into vacuum oven, it is permanent in 95 DEG C of constant temperature by being evacuated to -95MPa
Pressure baking, nitrogen charging to air pressure is -45MPa later；It vacuumizes, toast, inflated with nitrogen circulation implementation 9 hours, until moisture content contains in core
Amount≤200PPM；
(11.3) core is installed into steel shell, welds negative electrode lug and steel shell, be inserted into PIN steel pipe, Upper gasket, rolling are installed
Slot, test short circuit, injects 5.6g electrolyte, welds anode ear and nut cap, then nut cap and steel shell are fastened sealing and form battery core；Clearly
Wash battery core outer surface；Operations are 25 DEG C, complete in -38 DEG C~-41 DEG C of dew point of environment in environment temperature in this step.
(11.4) battery core is placed on after being activated 40 hours in the environment of temperature is 35 DEG C, is installed on formation cabinet and is changed
At being charged to 4.35V；Then aging five days in the environment of battery core is firstly placed on 30 DEG C of temperature carries out voltage internal resistance sieve to battery core
Choosing, screening battery core partial volume list charging voltage then aging five days in the environment of being placed on 25 DEG C of temperature, are made in the battery core of 3.6~3.9V
Lithium ion battery.
Embodiment 12:
The preparation method of lithium ion battery provided in this embodiment, includes the following steps:
(12.1) battery anode slice, battery cathode sheet are mounted on automatic winding-machine as requested respectively, using every
Battery anode slice and battery cathode sheet is isolated in film, while welding aluminium strip anode ear to battery anode slice, and battery cathode sheet welds nickel
It is wound after band negative electrode lug, core is made；The diaphragm is prepared by PP；
(12.2) core is inserted into jig, is put into vacuum oven, it is permanent in 80 DEG C of constant temperature by being evacuated to -88MPa
Pressure baking, nitrogen charging to air pressure is -65MPa later；It vacuumizes, toast, inflated with nitrogen circulation implementation 12 hours, until moisture content contains in core
Amount≤200PPM；
(12.3) core is installed into steel shell, welds negative electrode lug and steel shell, be inserted into PIN steel pipe, Upper gasket, rolling are installed
Slot, test short circuit, injects 5.4g electrolyte, welds anode ear and nut cap, then nut cap and steel shell are fastened sealing and form battery core；Clearly
Wash battery core outer surface；Operations are 25 DEG C, complete in -38 DEG C~-41 DEG C of dew point of environment in environment temperature in this step.
(12.4) battery core is placed on after being activated 48 hours in the environment of temperature is 35 DEG C, is installed on formation cabinet and is changed
At being charged to 4.5V；Then aging five days in the environment of battery core is firstly placed on 30 DEG C of temperature carries out voltage internal resistance screening to battery core,
Battery core partial volume list charging voltage is screened in the battery core of 3.6~3.9V, then aging five days in the environment of being placed on 25 DEG C of temperature, be made lithium from
Sub- battery.
It tests and analyzes:
Battery anode slice provided by selection example 1~4, battery cathode sheet provided by embodiment 5~8, embodiment 9
The preparation method of lithium ion battery provided by~11 manufactures 4 lithium ion battery samples, and specific combination refers to following table.It will
Lithium ion battery after preparing carries out the detection of safety check percent of pass, cycle performance, discharge platform, testing result following table institute
Show.
Detection data table
By the detection data of upper table it is found that being pressed using lithium ion battery sample 1~4 made of the embodiment of the present invention
Safety check test according to GBT 31485-2015 power accumulator safety requirements for electric vehicle and test method passed
100%, cycle performance is more outstanding (0.5C, which fills 1C, puts 600 weeks conservation rates all 89% or more), and thermal runaway stabilization is higher than
The prior art uses 50 DEG C or more as a positive electrode active material of ternary material, and the discharge platform of lithium ion battery is higher than the prior art
Using ternary material 0.1V as a positive electrode active material.Wherein, the battery core made in sample 2 is electronic according to GBT 31485-2015
Automobile power accumulator safety requirements and test method safety check test passed through 100%, cycle performance outstanding (600 weeks),
Discharge platform 3.7V is showed fitst water in the lithium ion battery of each sample.
In one preferred embodiment of the embodiment of the present invention, using stratiform nickel ion doped, single-walled carbon nanotube, gather inclined difluoro
The positive coating of battery anode slice is made in ethylene, using natural graphite, conductive black, sodium carboxymethylcellulose, butadiene-styrene rubber system
At the cathode coating of battery cathode sheet, make battery core made by the embodiment of the present invention (battery roll core) that there is at low cost, specific energy
Height, stability of material height, good cycle, the advantage that security performance is superior, sexual valence is high.In addition, using institute of the embodiment of the present invention
The preparation method of the preparation method of the battery anode slice of offer, the preparation method of battery cathode sheet and lithium ion battery is made
Battery anode slice, the water content of battery cathode sheet and battery roll core it is all relatively low, do not easily cause lithium ion battery short-circuit, into
And lithium ion battery provided by the embodiment of the present invention can be made to have the advantages that long service life, using safe.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and content, or directly/it is used in it indirectly
He is included in scope of patent protection of the invention relevant technical field.
Claims (10)
1. battery anode slice, including cathode metal substrate and coated on the positive coating outside the cathode metal substrate, it is described just
The component of pole coating includes positive active material, positive electrode binder, positive conductive agent, which is characterized in that the positive electrode active material
Matter is stratiform nickel ion doped LiNixMnyO2, wherein x=0.6~0.8, y=1-x.
2. battery anode slice as described in claim 1, which is characterized in that the anode coating includes the group of following parts by weight
Point:
Positive active material 98.34%~99.28%；
Positive conductive agent 0.02%~0.06%；
Positive electrode binder 0.7%~1.6%.
3. battery anode slice as claimed in claim 2, which is characterized in that
The anode coating includes the component of following parts by weight: positive active material 98.87%；Positive conductive agent 0.03%；
Positive electrode binder 1.1%；Alternatively,
The anode coating includes the component of following parts by weight: positive active material 98.75%；Positive conductive agent 0.05%；
Positive electrode binder 1.2%；Alternatively,
The anode coating includes the component of following parts by weight: positive active material 98.76%；Positive conductive agent 0.04%；
Positive electrode binder 1.2%；Alternatively,
The anode coating includes the component of following parts by weight: positive active material 98.8%；Positive conductive agent 0.05%；Just
Pole binder 1.15%.
4. battery anode slice as described in any one of claims 1 to 3, which is characterized in that
The positive conductive agent includes at least one of electrically conductive graphite, conductive carbon black, carbon fiber, carbon nanotube, graphene；
And/or
The positive electrode binder is polyvinylidene fluoride.
5. lithium ion battery, which is characterized in that including battery case, battery cathode sheet, the first diaphragm, the second diaphragm, electrolyte
With the described in any item battery anode slices of such as Claims 1-4, the battery anode slice, the battery cathode sheet, described first
Diaphragm, second diaphragm and the electrolyte are all set in the battery case, and the battery anode slice, the battery are negative
Pole piece, first diaphragm, second diaphragm are all dipped in the electrolyte, and the battery cathode sheet is being located at the battery just
Between pole piece and the battery case, first diaphragm is set between the battery anode slice and the battery cathode sheet, institute
The second diaphragm is stated to be set between the battery case and the battery cathode sheet.
6. lithium ion battery as claimed in claim 5, which is characterized in that the battery cathode sheet include negative metal substrate and
Coated on the cathode coating outside the negative metal substrate, the cathode coating includes following component in parts by weight:
Negative electrode active material 96.4%~98.2%；
Cathode conductive agent 0%-1%；
Suspending agent 0.8%~1.3%；
Negative electrode binder 1%~1.3%.
7. the preparation method of stratiform nickel ion doped, which comprises the steps of:
Nickel salt solution and manganese salt solution are mixed, metal salt solution is made；
The metal salt solution and enveloping agent solution, precipitant solution are subjected to precipitation reaction, solid-liquid mixed liquor is made；
The solid-liquid mixed liquor is separated by solid-liquid separation, solid spherical nickel-manganese binary presoma is obtained；
By the spherical nickel-manganese binary presoma and lithium source mixed sintering, broken, obtained sintering intermediate products；
It after the sintering intermediate products are carried out alumina-coated processing, then is sintered, is crushed, stratiform nickel ion doped is made
LiNixMnyO2, wherein x=0.6~0.8, y=1-x.
8. the preparation method of stratiform nickel ion doped as claimed in claim 7, which is characterized in that the nickel salt solution and manganese salt are molten
Being blended in the first container made of plating Teflon material for liquid carries out.
9. the preparation method of stratiform nickel ion doped as claimed in claim 7 or 8, which is characterized in that the metal salt solution with
The precipitation reaction of enveloping agent solution, the precipitant solution carries out in the second container equipped with bottom liquid and protective gas, described
Bottom liquid is water, ammonium hydroxide, sodium hydroxide, potassium hydroxide, any one or any combination in lithium hydroxide, and the bottom liquid
PH value is 10~12, and the protective gas is inert gas；And/or
The precipitation reaction embodiment of the metal salt solution and enveloping agent solution, the precipitant solution are as follows: by the metal
Salting liquid together with the enveloping agent solution, the precipitant solution cocurrent be added second container in carries out precipitation reaction, into
Continue heating, stirring after material, so that the metal salt solution continues to stop with the enveloping agent solution, the precipitant solution
It stays in and carries out precipitation reaction in the second container；And/or
The embodiment that the solid-liquid mixed liquor is separated by solid-liquid separation are as follows: the solid-liquid mixed liquor is separated by solid-liquid separation, it will
Solid material ageing obtained after separation, the solid material after ageing is separated by solid-liquid separation again, obtains the spherical shape
Nickel manganese binary presoma；And/or
The enveloping agent solution is ammonia spirit, and the precipitant solution is sodium hydroxide solution.
10. stratiform nickel ion doped, which is characterized in that using the system such as the described in any item stratiform nickel ion dopeds of claim 7 to 9
Preparation Method is made.
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