CN106848215B - A kind of high-tap density lithium ion battery ternary material and its preparation method and application - Google Patents
A kind of high-tap density lithium ion battery ternary material and its preparation method and application Download PDFInfo
- Publication number
- CN106848215B CN106848215B CN201611223385.3A CN201611223385A CN106848215B CN 106848215 B CN106848215 B CN 106848215B CN 201611223385 A CN201611223385 A CN 201611223385A CN 106848215 B CN106848215 B CN 106848215B
- Authority
- CN
- China
- Prior art keywords
- lithium
- nickel
- cobalt
- tap density
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000011164 primary particle Substances 0.000 claims abstract description 42
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000011026 diafiltration Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 5
- 229940009827 aluminum acetate Drugs 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- ONWSXQXQPJHQPU-UHFFFAOYSA-N ethane-1,2-diol;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OCCO.OC(=O)CC(O)(C(O)=O)CC(O)=O ONWSXQXQPJHQPU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract 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 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IUOOGQJPAJDLFV-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;ethane-1,2-diol Chemical compound OCCO.OC(=O)C(O)C(O)C(O)=O IUOOGQJPAJDLFV-UHFFFAOYSA-N 0.000 description 1
- YDQUROLTIDVHRK-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)CC(O)(C(O)=O)CC(O)=O YDQUROLTIDVHRK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910013410 LiNixCoyAlzO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- OUNMTQFEKAIZIF-UHFFFAOYSA-N ethane-1,2-diol;oxalic acid Chemical compound OCCO.OC(=O)C(O)=O OUNMTQFEKAIZIF-UHFFFAOYSA-N 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- VXIHMVAICSAJKM-UHFFFAOYSA-N oxalic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)C(O)=O VXIHMVAICSAJKM-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
-
- 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)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to field of batteries, and in particular to a kind of high-tap density lithium ion battery ternary material and its preparation method and application.Ternary material prepared by the present invention due to offspring addition so that the gap between primary particle is reduced, a large amount of offspring by fill or intercalation in a manner of enter, more crypto set is accumulated between particle, therefore the tap density of material is greatly improved.Due to the addition of primary particle, reduce the problem of offspring is reunited because of a large amount of accumulation, increase the availability of offspring, the effective area contacted between particle and electrolyte is also increased simultaneously, to improve the chemical property of material, including specific capacity, multiplying power and cycle characteristics.
Description
Technical field
The present invention relates to field of batteries, and in particular to a kind of high-tap density lithium ion battery ternary material and its preparation side
Method and application.
Background technique
Practical anode material for lithium-ion batteries can be roughly divided into three categories according to its structure at present: the first kind
It is the lithium metal oxide LiMO2 (M=Co, Ni, Mn) with six side's layer structures, representing material is cobalt acid lithium (LiCoO2)
With the sour lithium of ternary nickel cobalt manganese (NCM), the sour lithium material of nickel cobalt aluminium (NCA) (NCM:LiNixCoyMnzO2, x+y+z=1 and NCA:
LiNixCoyAlzO2, x+y+z=1)；Second class is the material with spinel structure, and representing material mainly has LiMn2O4；
Third class is the compound with polyanionic structure, and representing material mainly has the LiFePO 4 of olivine structural
LiFePO4.Wherein ternary material becomes a kind of great application prospect due to energy density with higher and low cost
Lithium ion battery material.But for the practical situations of ternary material, high rate performance and cycle performance need to be mentioned
It is high.
Summary of the invention
In view of the above problems, the present invention provides a kind of lithium ion battery ternary electrode material with high-tap density, tool
There are higher high rate performance and cycle performance.
The technical solution of present invention realization above-mentioned purpose are as follows: a kind of high-tap density lithium ion battery ternary material, it is described
High-tap density lithium ion battery ternary material includes nickel cobalt aluminic acid lithium material, nickel-cobalt lithium manganate material, the nickel cobalt lithium aluminate
Material is made of nickel cobalt lithium aluminate primary particle and nickel cobalt lithium aluminate offspring, and the nickel-cobalt lithium manganate material is by nickel cobalt mangaic acid
Lithium primary particle and nickle cobalt lithium manganate offspring composition.
The material is that the primary particle and offspring by NCA or NCM collectively constitute, relative to common ternary material
Material, due to the addition of offspring, so that the gap between primary particle is reduced, a large amount of offspring is to fill or intercalation
Mode enters, and more crypto set is accumulated between particle, therefore the tap density of material is greatly improved.Due to adding for primary particle
Enter, reduces the problem of offspring is reunited because of a large amount of accumulation, increase the availability of offspring, while
The effective area contacted between particle and electrolyte is increased, to improve the chemical property of material, including specific capacity, multiplying power
And cycle characteristics.
Further, by mass percentage: in the nickel cobalt aluminic acid lithium material, nickel cobalt lithium aluminate primary particle accounts for 30~
70%, surplus is nickel cobalt lithium aluminate offspring；In the nickel-cobalt lithium manganate material, nickle cobalt lithium manganate primary particle accounts for 30~
70%, surplus is nickle cobalt lithium manganate offspring.If if primary particle ratio not 30~70%, the specific volume of composite material
Amount is reduced, and high rate performance is obviously deteriorated.
Further, the size of the nickel cobalt lithium aluminate primary particle and nickle cobalt lithium manganate primary particle be 600~
The size of 800nm, the nickel cobalt lithium aluminate offspring and nickle cobalt lithium manganate offspring is 200~400nm.Present invention selection
Suitable particle, the material electrochemical performance prepared is more excellent, including specific capacity, multiplying power, cycle performance.
It is a further object to provide a kind of preparation method of high-tap density lithium ion battery ternary material, packets
Include step:
(1) lithium source, nickel source, cobalt source, silicon source, manganese source are distributed in deionized water and obtain solution A；
(2) citric acid-ethylene glycol aqueous solution is added in solution A, forms colloidal sol；The colloidal sol is dried to obtain bulk
Citric acid-glycerine, oxalic acid-ethylene glycol, tartaric acid-ethylene glycol, oxalic acid-glycerine, tartaric acid-the third three can be also added in gel
The aqueous solution of one of alcohol；
(3) deionized water is cleaned 3~5 times after crushing bulk gel obtained in step (2), and heating obtains primary particle
Presoma；
(4) deionized water is cleaned 3~5 times after crushing bulk gel obtained in step (2), then with organic solvent diafiltration
3~5 times, heating obtains offspring presoma, after organic solvent diafiltration, the metal residue and organic functional of particle surface
Group can remove, and grain diameter reduces.
(5) primary particle presoma and offspring presoma obtained in mixing step (3) and step (4), are calcined
Obtain high-tap density lithium ion battery ternary material；
Further, lithium source described in step (1) is one of lithium nitrate, lithium sulfate, lithium acetate or a variety of；The nickel
Source is one of nickel nitrate, nickel sulfate, nickel acetate or a variety of；The cobalt source is one of cobalt nitrate, cobaltous sulfate, cobalt acetate
Or it is a variety of；Source of aluminium is one of aluminum nitrate, aluminum sulfate, aluminum acetate or a variety of；The manganese source be manganese nitrate, manganese sulfate,
One of manganese acetate is a variety of.
Further, drying temperature is 120~160 DEG C in step (2).
Further, citric acid-ethylene glycol described in step (2) and the metal ion molar ratio in solution A are 1~1.2:
1.
Further, step (3) and heating temperature in step (4) are 300~600 DEG C, and heating time is 3~6h.
Further, calcination temperature is 600~1000 DEG C in step (5), and calcination time is 10~15h.
It is a further object to provide a kind of applications of high-tap density lithium ion battery ternary material, by three
First material and binder, conductive agent are uniformly mixed according to mass ratio for 6~8:0.8~1:1 ratio, and anode electrode is made.Together
Soft carbon is fabricated to negative electrode by the method for sample, is added three
First electrolyte is assembled into flexible packaged battery container.Chemical property, which is tested, in 0.5C and 5C multiplying power discharge capacity is respectively
166mAh/g and 129mAh/g, capacity attenuation rate is 8.9% after 2000 circulations.
The invention has the benefit that
Due to the addition of offspring so that the gap between primary particle is reduced, a large amount of offspring to fill or
The mode of intercalation enters, and more crypto set is accumulated between particle, therefore the tap density of material is greatly improved.Due to primary grain
The addition of son reduces the problem of offspring is reunited because of a large amount of accumulation, increases the availability of offspring,
The effective area contacted between particle and electrolyte is also increased simultaneously, to improve the chemical property of material, including specific volume
Amount, multiplying power and cycle characteristics.
Specific embodiment
The present invention is further detailed by the following examples.
Embodiment 1
Lithium nitrate, nickel sulfate, cobalt nitrate, aluminum nitrate, manganese nitrate are distributed in deionized water, are then added in the solution
The ratio of citric acid-glycol water, citric acid and metal ion is 1:1, is formed after gel and removes moisture removal at 120 DEG C.Then
By after drying blocky gel crush after use deionized water diafiltration 3 times, 300 DEG C heating 3 hours after obtain the forerunner of primary particle
Body.It is first used after equally the blocky gel after drying is crushed deionized water diafiltration 3 times, then uses surfactant sodium dodecyl base again
Benzene sulfonic acid diafiltration 3 times, 600 DEG C heating 3 hours after obtain the presoma of offspring.Obtained nickel cobalt lithium aluminate primary particle and
The size of nickle cobalt lithium manganate primary particle is 600nm, the size of nickel cobalt lithium aluminate offspring and nickle cobalt lithium manganate offspring
For 400nm.Then the two is mixed, nickle cobalt lithium manganate primary particle accounts for 70%, and surplus is nickle cobalt lithium manganate offspring, is placed in
It is calcined 15 hours at 600 DEG C and obtains ternary material.By ternary material obtained, binder PVDF and conductive agent acetylene black according to matter
Amount after mixing than 8:1:1, is fabricated to anode electrode.Graphite is fabricated to cathode by same method, is assembled into Soft Roll capacitor
Device.It is respectively 185mAh/g and 159mAh/g that chemical property, which is tested, in 0.5C and 5C multiplying power discharge capacity.
Embodiment 2
Lithium sulfate, nickel nitrate, cobalt nitrate, aluminum nitrate, manganese nitrate are distributed in deionized water, are then added in the solution
The ratio of citric acid-glycol water, citric acid and metal ion is 1.2:1, is formed after gel and removes moisture removal at 160 DEG C.So
Afterwards by after drying blocky gel crush after use deionized water diafiltration 3 times, 600 DEG C heating 5 hours after obtain primary particle before
Drive body.It is first used deionized water diafiltration 3 times after equally the blocky gel after drying is crushed, then uses surfactant sodium dodecyl again
Base benzene sulfonic acid diafiltration 3 times, 500 DEG C heating 5 hours after obtain the presoma of offspring.Obtained nickel cobalt lithium aluminate primary particle
Size with nickle cobalt lithium manganate primary particle is 700nm, the ruler of nickel cobalt lithium aluminate offspring and nickle cobalt lithium manganate offspring
Very little is 300nm.Then the two is mixed, nickle cobalt lithium manganate primary particle accounts for 60%, and surplus is nickle cobalt lithium manganate offspring, sets
It is calcined 12 hours at 800 DEG C and obtains ternary material.By ternary material obtained, binder PVDF and conductive agent acetylene black according to
Mass ratio 8:1:1 after mixing, is fabricated to anode electrode.Graphite is fabricated to cathode by same method, is assembled into Soft Roll electricity
Container.It is respectively 187mAh/g and 160mAh/g that chemical property, which is tested, in 0.5C and 5C multiplying power discharge capacity.
Embodiment 3
Lithium nitrate, nickel nitrate, cobalt nitrate, aluminum acetate, manganese nitrate are distributed in deionized water, are then added in the solution
The ratio of citric acid-glycol water, citric acid and metal ion is 1.1:1, is formed after gel and removes moisture removal at 140 DEG C.So
Afterwards by after drying blocky gel crush after use deionized water diafiltration 3 times, 400 DEG C heating 4 hours after obtain primary particle before
Drive body.It is first used deionized water diafiltration 3 times after equally the blocky gel after drying is crushed, then uses surfactant sodium dodecyl again
Base benzene sulfonic acid diafiltration 3 times, 400 DEG C heating 5 hours after obtain the presoma of offspring.Obtained nickel cobalt lithium aluminate primary particle
Size with nickle cobalt lithium manganate primary particle is 700nm, the ruler of nickel cobalt lithium aluminate offspring and nickle cobalt lithium manganate offspring
Very little is 300nm.Then the two is mixed, nickle cobalt lithium manganate primary particle accounts for 60%, and surplus is nickle cobalt lithium manganate offspring, sets
It is calcined 15 hours at 1000 DEG C and obtains ternary material.Ternary material obtained, binder PVDF and conductive agent acetylene black are pressed
After mixing according to mass ratio 7:0.9:1, it is fabricated to anode electrode.Graphite is fabricated to cathode by same method, is assembled into soft
Packet capacitor.It is respectively 183mAh/g and 154mAh/g that chemical property, which is tested, in 0.5C and 5C multiplying power discharge capacity.
Embodiment 4
Lithium nitrate, nickel nitrate, cobalt nitrate, aluminum acetate, manganese nitrate are distributed in deionized water, are then added in the solution
The ratio of citric acid-glycol water, citric acid and metal ion is 1:1, is formed after gel and removes moisture removal at 160 DEG C.Then
By after drying blocky gel crush after use deionized water diafiltration 3 times, 600 DEG C heating 3 hours after obtain the forerunner of primary particle
Body.It is first used after equally the blocky gel after drying is crushed deionized water diafiltration 3 times, then uses surfactant sodium dodecyl base again
Benzene sulfonic acid diafiltration 3 times, 300 DEG C heating 3 hours after obtain the presoma of offspring.Obtained nickel cobalt lithium aluminate primary particle and
The size of nickle cobalt lithium manganate primary particle is 800nm, the size of nickel cobalt lithium aluminate offspring and nickle cobalt lithium manganate offspring
For 200nm.Then the two is mixed, nickle cobalt lithium manganate primary particle accounts for 70%, and surplus is nickle cobalt lithium manganate offspring, is placed in
It is calcined 12 hours at 900 DEG C and obtains ternary material.By ternary material obtained, binder PVDF and conductive agent acetylene black according to matter
Amount after mixing than 6:1:1, is fabricated to anode electrode.Graphite is fabricated to cathode by same method, is assembled into Soft Roll capacitor
Device.It is respectively 188mAh/g and 162mAh/g that chemical property, which is tested, in 0.5C and 5C multiplying power discharge capacity.
Embodiment 5
Lithium nitrate, nickel nitrate, cobalt nitrate, aluminum acetate, manganese nitrate are distributed in deionized water, are then added in the solution
The ratio of citric acid-glycol water, citric acid and metal ion is 1.2:1, is formed after gel and removes moisture removal at 160 DEG C.So
Afterwards by after drying blocky gel crush after use deionized water diafiltration 3 times, 300 DEG C heating 3 hours after obtain primary particle before
Drive body.It is first used deionized water diafiltration 3 times after equally the blocky gel after drying is crushed, then uses surfactant sodium dodecyl again
Base benzene sulfonic acid diafiltration 3 times, 600 DEG C heating 3 hours after obtain the presoma of offspring.Obtained nickel cobalt lithium aluminate primary particle
Size with nickle cobalt lithium manganate primary particle is 800nm, the ruler of nickel cobalt lithium aluminate offspring and nickle cobalt lithium manganate offspring
Very little is 200nm.Then the two is mixed, nickle cobalt lithium manganate primary particle accounts for 70%, and surplus is nickle cobalt lithium manganate offspring, sets
It is calcined 10 hours at 1000 DEG C and obtains ternary material.Ternary material obtained, binder PVDF and conductive agent acetylene black are pressed
After mixing according to mass ratio 8:0.8:1, it is fabricated to anode electrode.Graphite is fabricated to cathode by same method, is assembled into soft
Packet capacitor.It is respectively 183mAh/g and 167mAh/g that chemical property, which is tested, in 0.5C and 5C multiplying power discharge capacity.
This place embodiment is not exhaustive claimed midpoint of technical range and in embodiment technology
In scheme to single or multiple technical characteristics it is same replacement be formed by new technical solution, equally all the present invention claims
In the range of protection；Simultaneously the present invention program it is all enumerate or unlisted embodiment in, in the same embodiment each
Parameter is merely representative of an example (i.e. a kind of feasible scheme) for its technical solution, and between parameters and is not present stringent
Cooperation and qualified relation, wherein each parameter can be replaced mutually when stating and asking without prejudice to axiom and the present invention, special declaration
Except.
The technical means disclosed in the embodiments of the present invention is not limited to the technical means disclosed in the above technical means, and further includes
Technical solution consisting of any combination of the above technical features.The foregoing is a specific embodiment of the present invention, should refer to
Out, for those skilled in the art, without departing from the principle of the present invention, can also make several
Improvements and modifications, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (9)
1. a kind of high-tap density lithium ion battery ternary material, it is characterised in that: the high-tap density lithium ion battery three
First material includes nickel cobalt aluminic acid lithium material, nickel-cobalt lithium manganate material, and the nickel cobalt aluminic acid lithium material is by the primary grain of nickel cobalt lithium aluminate
Son and nickel cobalt lithium aluminate offspring composition, the nickel-cobalt lithium manganate material is by nickle cobalt lithium manganate primary particle and nickle cobalt lithium manganate
Offspring composition；
The preparation method of the high-tap density lithium ion battery ternary material, comprising steps of
(1) lithium source, nickel source, cobalt source, silicon source, manganese source are distributed in deionized water and obtain solution A；
(2) citric acid-ethylene glycol aqueous solution is added in solution A, forms colloidal sol；The colloidal sol is dried to obtain blocky solidifying
Glue；
(3) deionized water is cleaned 3~5 times after crushing bulk gel obtained in step (2), and heating obtains primary particle forerunner
Body；
(4) deionized water is cleaned 3~5 times after crushing bulk gel obtained in step (2), then with organic solvent diafiltration 3~5
Secondary, heating obtains offspring presoma；
(5) primary particle presoma and offspring presoma obtained in mixing step (3) and step (4), calcining obtain height
Tap density lithium ion battery ternary material.
2. a kind of high-tap density lithium ion battery ternary material according to claim 1, it is characterised in that: press quality hundred
Point ratio: in the nickel cobalt aluminic acid lithium material, nickel cobalt lithium aluminate primary particle accounts for 30~70%, and surplus is the secondary grain of nickel cobalt lithium aluminate
Son；In the nickel-cobalt lithium manganate material, nickle cobalt lithium manganate primary particle accounts for 30~70%, and surplus is the secondary grain of nickle cobalt lithium manganate
Son.
3. a kind of high-tap density lithium ion battery ternary material according to claim 1, it is characterised in that: the nickel cobalt
The size of lithium aluminate primary particle and nickle cobalt lithium manganate primary particle be 600~800nm, the nickel cobalt lithium aluminate offspring and
The size of nickle cobalt lithium manganate offspring is 200~400nm.
4. a kind of high-tap density lithium ion battery ternary material according to claim 1, it is characterised in that: step (1)
Described in lithium source be one of lithium nitrate, lithium sulfate, lithium acetate or a variety of；The nickel source is nickel nitrate, nickel sulfate, nickel acetate
One of or it is a variety of；The cobalt source is one of cobalt nitrate, cobaltous sulfate, cobalt acetate or a variety of；Source of aluminium be aluminum nitrate,
One of aluminum sulfate, aluminum acetate are a variety of；The manganese source is one of manganese nitrate, manganese sulfate, manganese acetate or a variety of.
5. a kind of high-tap density lithium ion battery ternary material according to claim 1, it is characterised in that: step (2)
Middle drying temperature is 120~160 DEG C.
6. a kind of high-tap density lithium ion battery ternary material according to claim 1, it is characterised in that: step (2)
Described in metal ion molar ratio in citric acid-ethylene glycol and solution A be 1~1.2:1.
7. a kind of high-tap density lithium ion battery ternary material according to claim 1, it is characterised in that: step (3)
It is 300~600 DEG C with heating temperature in step (4), heating time is 3~6h.
8. a kind of high-tap density lithium ion battery ternary material according to claim 1, it is characterised in that: step (5)
Middle calcination temperature is 600~1000 DEG C, and calcination time is 10~15h.
9. a kind of capacitor, it is characterised in that: by high-tap density lithium ion battery ternary material as described in claim 1 with
Binder, conductive agent are uniformly mixed according to mass ratio for 6~8:0.8~1:1, and anode electrode is made, positive electrode and negative electrode are assembled
Obtain capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611223385.3A CN106848215B (en) | 2016-12-27 | 2016-12-27 | A kind of high-tap density lithium ion battery ternary material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611223385.3A CN106848215B (en) | 2016-12-27 | 2016-12-27 | A kind of high-tap density lithium ion battery ternary material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106848215A CN106848215A (en) | 2017-06-13 |
| CN106848215B true CN106848215B (en) | 2019-09-13 |
Family
ID=59135570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611223385.3A Active CN106848215B (en) | 2016-12-27 | 2016-12-27 | A kind of high-tap density lithium ion battery ternary material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106848215B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706373B (en) * | 2017-09-19 | 2020-05-22 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery high nickel ternary material and preparation method thereof |
| CN110416511B (en) | 2019-07-19 | 2020-12-25 | 宁德新能源科技有限公司 | Positive electrode material, and positive electrode and electrochemical device comprising same |
| CN116404160B (en) * | 2023-03-28 | 2024-06-21 | 江门市科恒实业股份有限公司 | High-Wen Mengsuan-resistant lithium positive electrode material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101117623B1 (en) * | 2009-06-05 | 2012-02-29 | 에스비리모티브 주식회사 | Positive electrode for rechargeable lithium battery and rechargeable lithium battery including the positive electrode |
| CN103943822B (en) * | 2014-05-13 | 2017-03-29 | 南通瑞翔新材料有限公司 | A kind of lithium rechargeable battery nickel-base anode active material and preparation method thereof |
| CN107316995A (en) * | 2017-05-27 | 2017-11-03 | 广东烛光新能源科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN107316997A (en) * | 2017-05-27 | 2017-11-03 | 广东烛光新能源科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof |
-
2016
- 2016-12-27 CN CN201611223385.3A patent/CN106848215B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106848215A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10522816B2 (en) | Lithium secondary battery | |
| CN111435740B (en) | Positive electrode active material, positive electrode sheet and sodium ion battery | |
| KR101811935B1 (en) | Non-aqueous electrolyte secondary battery | |
| CN111200109B (en) | Battery with a battery cell | |
| EP3588630A1 (en) | Positive electrode plate and lithium ion battery | |
| CN102292851B (en) | Positive electrode for lithium secondary battery, and process for producing same | |
| CN102544481B (en) | Lithium ion battery and cathode material thereof | |
| WO2017190367A1 (en) | Secondary battery and preparation method therefor | |
| US9263729B2 (en) | Lithium secondary battery | |
| Yang et al. | Understanding voltage decay in lithium-rich manganese-based layered cathode materials by limiting cutoff voltage | |
| CN105161693B (en) | A kind of high circulation lithium electricity polynary positive pole material NCM and preparation method thereof | |
| KR101980974B1 (en) | Method for producing negative electrode and secondary battery, and secondary battery | |
| CN111200159B (en) | Battery with a battery cell | |
| CN111799470B (en) | Positive pole piece and sodium ion battery | |
| CN103117410B (en) | 1.5V rechargeable lithium battery and preparation method thereof | |
| JP7211900B2 (en) | Positive electrode material for secondary battery, and secondary battery using the same | |
| CN102290577A (en) | A negative electrode of a lithium ion battery | |
| KR20200096736A (en) | Anode layer and all solid state battery | |
| CN106848215B (en) | A kind of high-tap density lithium ion battery ternary material and its preparation method and application | |
| CN109860584B (en) | High-energy density lithium ion secondary battery | |
| CN106953073A (en) | Lithium iron phosphate anode composite material and preparation method thereof | |
| CN100466343C (en) | Positive electrode active material composition, positive electrode sheet and lithium ion battery | |
| JP2015088343A (en) | Method for manufacturing positive electrode active material for nonaqueous electrolyte secondary batteries | |
| EP3641025A1 (en) | Secondary battery | |
| JP2005197073A (en) | Positive electrode for lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |