CN107221656A - A kind of lithium ion battery rich lithium manganese base solid solution positive electrode and preparation method thereof - Google Patents
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode and preparation method thereof Download PDFInfo
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- CN107221656A CN107221656A CN201710423018.6A CN201710423018A CN107221656A CN 107221656 A CN107221656 A CN 107221656A CN 201710423018 A CN201710423018 A CN 201710423018A CN 107221656 A CN107221656 A CN 107221656A
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- positive electrode
- solid solution
- manganese base
- base solid
- lithium manganese
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- 239000006104 solid solution Substances 0.000 title claims abstract description 122
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 110
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 26
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 23
- 238000009826 distribution Methods 0.000 claims abstract description 18
- 229910014733 LiNiaCobMncO2 Inorganic materials 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 239000012266 salt solution Substances 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 40
- 229910052744 lithium Inorganic materials 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 29
- 229910052748 manganese Inorganic materials 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 18
- 239000008139 complexing agent Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 238000005245 sintering Methods 0.000 description 12
- 239000010405 anode material Substances 0.000 description 10
- 239000010406 cathode material Substances 0.000 description 8
- 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 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910000651 0.4Li2MnO3 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001346 0.5Li2MnO3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- H01M4/48—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium ion battery rich lithium manganese base solid solution positive electrode and preparation method thereof, the chemical general formula of the rich lithium manganese base solid solution positive electrode is：xLi2MnO3·(1‑x)LiNiaCobMncO2, wherein 0.2≤x≤0.7, a+b+c=1,0.2≤a≤0.8,0.1≤c≤0.5；It is closely knit inside the particle of the rich lithium manganese base solid solution positive electrode, without hollow phenomenon, tap density TD>2.0g/cm3, size distribution COEFFICIENT K90For 0.6~0.9, wherein K90=(D90‑D10)/D50.Closely knit, particle size distribution is narrow inside good sphericity of the present invention, particle, the chemical properties such as its capacity, cycle life can significantly improve, and its preparation method is without using complexing agent, preparation technology is simple, the easy stability contorting of process, production cost are low, environment friendly and pollution-free, is adapted to large-scale industrial production.
Description
Technical field
The present invention relates to field of lithium ion battery anode, more particularly to a kind of lithium-rich manganese-based solid solution of lithium ion battery
Body positive electrode and preparation method thereof.
Background technology
Lithium ion battery is that one kind has the advantages that higher energy density, recyclable charge and discharge, environment-friendly, memory-less effect
Electrochmical power source, one of be hybrid power with pure electric power power supply.At present, conventional several anode material for lithium-ion batteries are (such as：
LiCoO2、LiPeO4And LiNi1/3Mn1/3Co1/3O2Deng) requirement of the lithium ion battery to high-energy-density can not be met, particularly
The requirement of lithium ion battery used for electric vehicle can not be met.Rich lithium manganese base solid solution positive electrode xLi2MnO3·(1-x)LiMO2
(M=Co, Ni, Mn at least one) has very high specific capacity, therefore is considered as to be moved for the pure of long course continuation mileage in future
One of preferable positive electrode of power power supply (EV) and hybrid power power supply (HEV).
Rich lithium manganese base solid solution positive electrode is under higher charging voltage, with very high specific capacity, but it is in big electricity
Flow capacity attenuation under condition of work very fast, substantially, this restrict the commercialization of rich lithium manganese base solid solution positive electrode for polarization phenomena
Using.Improve the electronic conductivity and Li of positive electrode+Migration rate can reduce polarization, greatly improve the reversible appearance of battery
Amount and high rate performance.And it is to control lithium ion in material internal to adjust material granule particles size and distribution, interior solid, pattern
One of and the effective method of diffusion velocity at interface.The density of Mn based materials is generally relatively low, and not fine and close enough inside particle, this causes
Occurs micro-crack after multiple discharge and recharge inside particle, internal resistance increase has had a strong impact on the cycle performance of material.In addition, using altogether
The rich lithium manganese base solid solution positive electrode material precursor of precipitation method synthesis, will not substantially change in the sintering process after adding lithium source
Become material density, pattern and granularity, therefore rich lithium manganese base solid solution positive electrode material precursor synthesis technique largely
On determine the chemical property of material, that is to say, that structure and chemical property of the suitable synthetic method of selection to material
Also have a great impact.
Chinese patent CN102916176B discloses a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode and its preparation
The rich lithium manganese base solid solution positive electrode particle sphericity obtained in method, patent is poor, and particle surface is rough, and size distribution is not
Uniformly, and in preparation method ammoniacal liquor is employed as complexing agent, there are problems that the environmental protection treatment of ammonia nitrogen.Chinese patent
CN103474646B discloses a kind of mesh structural porous lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof, will in patent
Lithium salts, nickel salt, manganese salt, cobalt salt are dissolved in deionized water by a certain percentage, appropriate sucrose are added as complexing agent, by solution
Heating evaporation obtains colloidal sol finally to gel, then calcines, obtained mesh structural porous lithium-rich manganese-based anode material for lithium-ion batteries
For aspherical porous particle, density is low, although capacity is higher, and preferably, cycle performance is poor, volume energy density for high rate performance
It is low.Chinese patent application 201510355184.8 discloses a kind of lithium ion battery lithium-rich manganese-based anode with hollow-core construction
Metal salt solution, precipitating reagent, complexing agent are mixed to add in material and preparation method thereof, patent and are co-precipitated in reaction
Presoma, is calcined after then presoma is mixed with lithium compound, have inside obtained lithium-rich manganese-based anode material particle it is hollow,
Size distribution is wide, sphericity is poor, easily produces micro-crack in charge and discharge process inside particle, influences cycle performance, and prepare
The complexing agent containing ammonia nitrogen is employed in method, there is environmental issue.Chinese patent CN104218238B discloses a kind of rich lithium
Mixed after the urea that the aqueous solution of metal salt mixture is added to scheduled volume in the preparation method of manganese-based anode material, patent
Solution, under agitation reaction obtains the reaction system containing the first sediment；(NH is added dropwise into the system4)2CO3
The aqueous solution, after reaction carry out be evaporated processing, obtain the presoma containing Li, Ni, Mn and M, be then ground, sinter, obtain
The lithium-rich manganese-based anode material particle sphericity arrived is poor, rough, has a large amount of fine powders, size distribution is wide, and the side of preparation
The urea, (NH used in method4)2CO3Contain ammonia nitrogen, there is environmental issue.
The content of the invention
In order to solve lithium ion battery rich lithium manganese base solid solution positive electrode in the prior art exist particle sphericity it is poor,
The wide technical problem of leakiness, particle size distribution inside particle, the invention provides a kind of lithium ion battery with lithium-rich manganese-based
Solid solution cathode material and preparation method thereof.The lithium ion battery that the present invention is provided rich lithium manganese base solid solution anode material spherical
Spend, closely knit, particle size distribution is narrow inside particle, so that the chemical property such as its capacity, cycle life can be obtained significantly
Improve.And the lithium ion battery that provides of the present invention with the preparation method of rich lithium manganese base solid solution positive electrode not only without using network
Mixture, and preparation technology is simple, the easy stability contorting of process, production cost are low, environment friendly and pollution-free, is adapted to heavy industrialization
Production.
The purpose of the present invention is achieved through the following technical solutions：
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its chemical general formula is：xLi2MnO3·(1-x)
LiNiaCobMncO2, wherein 0.2≤x≤0.7, a+b+c=1,0.2≤a≤0.8,0.1≤c≤0.5；It is described lithium-rich manganese-based solid
Closely knit, tap density TD inside the particle of solution positive electrode>2.0g/cm3, size distribution COEFFICIENT K90For 0.6~0.9, wherein
K90=(D90-D10)/D50。
Preferably, the mean particle size D of described rich lithium manganese base solid solution positive electrode50For 4 μm~15 μm.
A kind of lithium ion battery preparation method of rich lithium manganese base solid solution positive electrode, comprises the following steps：
Step A, the chemical general formula xLi according to rich lithium manganese base solid solution positive electrode2MnO3·(1-x)LiNiaCobMncO2
In manganese, nickel, cobalt mol ratio, manganese salt, nickel salt, cobalt salt are mixed, be configured to metal ion total concentration for 0.5~
3mol/L metal mixed salt solution；Wherein, 0.2≤x≤0.7, a+b+c=1,0.2≤a≤0.8,0.1≤c≤0.5；
It is step B, while stirring that the metal mixed salt solution and concentration is molten for 0.5~2.5mol/L carbonate
Liquid cocurrent is added in reactor, and the pH value for making reaction solution is 7.5~8.5, and controlling reaction temperature is 35~60 DEG C, reaction time
For 6~60h, so that the presoma slurries of rich lithium manganese base solid solution positive electrode are made；
Step C, the presoma slurries to the rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to solid-liquid point
Cleaned and dried from obtained solid, then crossed 300~500 mesh sieves and sieved, so as to obtain presoma；
Step D, the chemical general formula xLi according to rich lithium manganese base solid solution positive electrode2MnO3·(1-x)LiNiaCobMncO2
Middle lithium and manganese, nickel, the mol ratio of cobalt, the presoma is uniformly mixed with lithium source, and 6~25h of sintering at 780~950 DEG C,
Then crushed and sieved, so that above-mentioned lithium ion battery rich lithium manganese base solid solution positive electrode is made.
Preferably, in stepb, it is described while stirring by the metal mixed salt solution and concentration be 0.5~
2.5mol/L carbonate solution cocurrent, which is added to reactor, to be included：Deionization is added in the reactor with agitating paddle
Water, makes the ionized water in reactor not have the blade of agitating paddle, then under 500~1000rpm speed of agitator, by the gold
Category mixed salt solution and concentration are added in reactor for 0.5~2.5mol/L carbonate solution cocurrent, control the metal
Mixed salt solution and the carbonate solution add flow velocity, and the pH value for making reaction solution is 7.5~8.5.
Preferably, in step C, it is described the solid that separation of solid and liquid is obtained is cleaned and dried including：To solid-liquid
Isolated solid is cleaned, and 2~20h is then dried at 100~150 DEG C.
Preferably, in step, the anion of the metal mixed salt solution is sulfate ion, salt acid ion, nitre
At least one of acid ion, acetate ion.
Preferably, in stepb, the reaction time is 12~48h.
Preferably, in stepb, the carbonate solution is Na2CO3、K2CO3At least one of.
Preferably, in step E, the lithium source is Li2CO3, at least one of LiOH.
As seen from the above technical solution provided by the invention, the lithium ion battery that provides of the present invention is with lithium-rich manganese-based solid
Solution positive electrode is by adjusting chemical general formula xLi2MnO3·(1-x)LiNiaCobMncO2Middle lithium, manganese, nickel, the mol ratio of cobalt,
And control inside particle it is closely knit, without hollow, size distribution COEFFICIENT K90For 0.6~0.9, K90=(D90-D10)/D50, so that should
Lithium ion battery is with rich lithium manganese base solid solution anode material spherical degree is good, closely knit, particle size distribution is narrow inside particle, and it holds
The chemical properties such as amount, cycle life can significantly improve.Lithium ion battery rich lithium manganese base solid solution positive electrode
Preparation method, eliminate the use of complexing agent, directly synthesized using manganese, nickel, cobalt metal salt solution and carbonate solution,
By selecting suitable process conditions to prepare the larger and closely knit presoma of good sphericity, granularity.Due to do not use containing
The complexing agent of ammonia nitrogen, it is to avoid traditional co-precipitation method uses ammoniacal liquor, ammonium salt etc. for complexing agent pollution on the environment, also avoids
Use the cost of material of complexing agent.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, being used required in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the scanning electron microscope (SEM) photograph of rich lithium manganese base solid solution positive electrode in the embodiment of the present invention 1.
Fig. 2 is the section electron microscope of rich lithium manganese base solid solution positive electrode particle in the embodiment of the present invention 1.
Fig. 3 is the 2.0-4.6V cyclic curve figures of rich lithium manganese base solid solution positive electrode in the embodiment of the present invention 1.
Embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
The embodiment of invention, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
Below to lithium ion battery provided in an embodiment of the present invention rich lithium manganese base solid solution positive electrode and its preparation side
Method is described in detail.
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its chemical general formula is：xLi2MnO3·(1-x)
LiNiaCobMncO2, wherein 0.2≤x≤0.7, a+b+c=1,0.2≤a≤0.8,0.1≤c≤0.5；It is described lithium-rich manganese-based solid
Closely knit, tap density TD inside the particle of solution positive electrode>2.0g/cm3, size distribution COEFFICIENT K90For 0.6~0.9, wherein
K90=(D90-D10)/D50.The mean particle size D of described rich lithium manganese base solid solution positive electrode50For 4 μm~15 μm, and the richness
Lithium manganese based solid solution positive electrode particle is preferably spherical.
Specifically, the preparation method of the lithium ion battery rich lithium manganese base solid solution positive electrode comprises the following steps：
Step A, the chemical general formula xLi according to rich lithium manganese base solid solution positive electrode2MnO3·(1-x)LiNiaCobMncO2
In manganese, nickel, cobalt mol ratio, manganese salt, nickel salt, cobalt salt are mixed, be configured to metal ion total concentration for 0.5~
3mol/L metal mixed salt solution；Wherein, 0.2≤x≤0.7, a+b+c=1,0.2≤a≤0.8,0.1≤c≤0.5.In reality
In the application of border, the anion of the metal mixed salt solution is sulfate ion, salt acid ion, nitrate ion, acetate
At least one of ion, that is to say, that these metal salts can be sulfate, hydrochloride, nitrate, acetate at least
It is a kind of.
It is step B, while stirring that the metal mixed salt solution and concentration is molten for 0.5~2.5mol/L carbonate
Liquid cocurrent is added in reactor, and the pH value for making reaction solution is 7.5~8.5, and controlling reaction temperature is 35~60 DEG C, reaction time
For 6~60h (preferably 12~48h), so that the presoma slurries of rich lithium manganese base solid solution positive electrode are made.Wherein, it is described
The metal mixed salt solution and concentration are added to instead for 0.5~2.5mol/L carbonate solution cocurrent while stirring
Kettle is answered to include：Deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had agitating paddle
Blade, is 0.5~2.5mol/L by the metal mixed salt solution and concentration then under 500~1000rpm speed of agitator
Carbonate solution cocurrent be added in reactor, control the metal mixed salt solution and the carbonate solution to add stream
Speed, the pH value for making reaction solution is 7.5~8.5.In actual applications, the carbonate solution can be Na2CO3、K2CO3In
It is at least one.
Step C, the presoma slurries to the rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to solid-liquid point
Cleaned and dried from obtained solid, then crossed 300~500 mesh sieves and sieved, so as to obtain presoma.Wherein, institute
State the solid that separation of solid and liquid is obtained is cleaned and dried including：The solid obtained using pure water to separation of solid and liquid carries out clear
Wash, 2~20h is then dried at 100~150 DEG C.
Step D, the chemical general formula xLi according to rich lithium manganese base solid solution positive electrode2MnO3·(1-x)LiNiaCobMncO2
Middle lithium and manganese, nickel, the mol ratio of cobalt, the presoma is uniformly mixed with lithium source, and 6~25h of sintering at 780~950 DEG C,
Then crushed and sieved, so that above-mentioned lithium ion battery rich lithium manganese base solid solution positive electrode is made.Wherein, it is described
Lithium source is Li2CO3, at least one of LiOH.
Compared with prior art, lithium ion battery provided by the present invention rich lithium manganese base solid solution positive electrode and its system
Preparation Method at least has advantages below：
(1) lithium ion battery provided by the present invention rich lithium manganese base solid solution positive electrode narrow particle size distribution, Neng Gouyou
Imitate hoist capacity and cycle performance.Due to the sintering temperature of the small positive electrode particle of particle diameter and the big positive electrode particle of particle diameter
Differ greatly, the positive electrode of wide size distribution can cause the chemical property of positive electrode not using identical sintering temperature
Good, excessive particle reduces the capacity of positive electrode, and too small particle reduces the cycle performance of positive electrode, narrow particle size distribution
Rich lithium manganese base solid solution positive electrode can be prevented effectively from problem above.
(2) lithium ion battery provided by the present invention closely knit, nothing inside the particle of rich lithium manganese base solid solution positive electrode
Hollow phenomenon, can effectively improve diffusion velocity of the lithium ion in material internal, so that hoist capacity and high rate performance, and material
The density of material is high, and volume energy density is also accordingly improved.
(3) lithium ion battery provided by the present invention its particle good sphericity of rich lithium manganese base solid solution positive electrode,
Grain surface is smooth, without the fine powder largely adhered to, can effectively improve the processing of positive electrode slurry during positive plate is made
Performance, while reducing the reactivity of positive electrode surface and electrolyte, and then improves cycle performance and security performance.
(4) the lithium ion battery provided by the present invention preparation method of rich lithium manganese base solid solution positive electrode, is eliminated
The use of complexing agent, is directly synthesized using manganese, nickel, cobalt metal salt solution and carbonate solution, suitable anti-by selection
Answer the process conditions such as liquid pH value, reaction temperature, reaction time can prepare good sphericity, granularity it is larger and closely knit before
Drive body.Due to not using the complexing agent containing ammonia nitrogen, it is to avoid it is complexing agent to ring that traditional co-precipitation method, which uses ammoniacal liquor, ammonium salt etc.,
The pollution that border is caused, it also avoid the cost of material using complexing agent.
As fully visible, the lithium ion battery in the embodiment of the present invention with rich lithium manganese base solid solution anode material spherical degree it is good,
Closely knit, particle size distribution is narrow inside particle, so that the chemical property such as its capacity, cycle life can significantly improve.
And the lithium ion battery in the embodiment of the present invention with the preparation method of rich lithium manganese base solid solution positive electrode not only without using network
Mixture, and preparation technology is simple, the easy stability contorting of process, production cost are low, environment friendly and pollution-free, is adapted to heavy industrialization
Production.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with tool
Lithium ion battery rich lithium manganese base solid solution positive electrode and preparation method thereof in the present invention is described in detail body embodiment.
Embodiment 1
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its preparation method comprises the following steps：
Step a1, according to rich lithium manganese base solid solution positive electrode chemical general formula 0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/ 3O2In manganese, nickel, cobalt mol ratio, manganese chloride, nickel sulfate, cobalt chloride are mixed, being configured to metal ion total concentration is
3mol/L metal mixed salt solution.
Step b1, deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had stirring
The blade of oar, then under 800rpm speed of agitator, by the carbonic acid that the metal mixed salt solution and concentration are 0.5mol/L
Sodium solution continues cocurrent and is added in reactor, controls the metal mixed salt solution and the sodium carbonate liquor to add stream respectively
Speed, the pH value for making reaction solution is 7.6~7.7, and controlling reaction temperature is 50 DEG C, the reaction time is 20h, so as to be made lithium-rich manganese-based
The presoma slurries of solid solution cathode material.
Step c1, the presoma slurries to the rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to solid-liquid
Isolated solid is cleaned, and 16h is then dried at 110 DEG C, is sieved after 300 mesh sieves, so as to obtain forerunner
Body.
Step d1, according to Mn, Ni, Co three summation and Li mol ratio it is 1:1.4 ratio, by the presoma with
LiOH is uniformly mixed, and then Temperature fall and is crushed with 900 DEG C of sintering 8h in air atmosphere, it is broken after cross 400 mesh sieves and enter
Row screening, so that rich lithium manganese base solid solution positive electrode 0.4Li is made2MnO3·0.6LiNi1/3Co1/3Mn1/3O2。
Specifically, following observation is carried out to the rich lithium manganese base solid solution positive electrode in the embodiment of the present invention 1 and is measured：
(1) rich lithium manganese base solid solution positive electrode made from the step d1 of the embodiment of the present invention 1 is detected, can obtained
Go out obtained rich lithium manganese base solid solution positive electrode, its mean particle size D in the embodiment of the present invention 150=11.6 μm, K90=0.83,
Tap density is 2.35g/cm3。
(2) rich lithium manganese base solid solution positive electrode made from the step d1 of the embodiment of the present invention 1 is detected, so that
To scanning electron microscope (SEM) photograph as shown in Figure 1 and particle section electron microscope as shown in Figure 2.It can be seen that by Fig. 1 and Fig. 2：The present invention
Obtained rich lithium manganese base solid solution positive electrode is closely knit inside the homogeneous sphere material of quality, particle in embodiment 1.
(3) 2032 types are made using rich lithium manganese base solid solution positive electrode made from the step d1 of the embodiment of the present invention 1 to buckle
Formula battery, and charge and discharge electro-detection is carried out using new prestige battery test system, voltage range is 2.0~4.6V, first charge-discharge electricity
Current density is 20mAg-1, using current density as 40mAg-1Cycle performance test is carried out, test temperature is 25 DEG C, so that
To 2.0-4.6V cyclic curve figures as shown in Figure 3.As seen from Figure 3：Using lithium-rich manganese-based solid solution in the embodiment of the present invention 1
2032 type button cells are made in body positive electrode, and first discharge specific capacity is 276.8mAh/g, capability retention after circulating 50 weeks
For 97.3%.
Embodiment 2
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its preparation method comprises the following steps：
Step a2, according to rich lithium manganese base solid solution positive electrode chemical general formula 0.6Li2MnO3·
0.4LiNi0.5Co0.2Mn0.3O2In manganese, nickel, cobalt mol ratio, manganese sulfate, nickel sulfate, cobaltous sulfate are mixed, are configured to
Metal ion total concentration is 2mol/L metal mixed salt solution.
Step b2, deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had stirring
The blade of oar, then under 700rpm speed of agitator, by the sodium carbonate that the metal mixed salt solution and concentration are 2mol/L
Solution continues cocurrent and is added in reactor, controls the metal mixed salt solution and the sodium carbonate liquor to add stream respectively
Speed, the pH value for making reaction solution is 8.3~8.4, and controlling reaction temperature is 60 DEG C, the reaction time is 20h, so as to be made lithium-rich manganese-based
The presoma slurries of solid solution cathode material.
Step c2, the presoma slurries to rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to separation of solid and liquid
Obtained solid is cleaned, and 8h is then dried at 130 DEG C, is sieved after 300 mesh sieves, so as to obtain presoma.
Step d2, according to Mn, Ni, Co three summation and Li mol ratio it is 1:1.6 ratio, by the presoma and carbon
Sour lithium is uniformly mixed, and in air atmosphere with 830 DEG C of sintering 18h, then Temperature fall and is crushed, it is broken after cross 400 mesh sieves and enter
Row screening, so that rich lithium manganese base solid solution positive electrode 0.6Li is made2MnO3·0.4LiNi0.5Co0.2Mn0.3O2。
Specifically, rich lithium manganese base solid solution positive electrode made from the step d2 of the embodiment of the present invention 2 is detected, can
To draw obtained rich lithium manganese base solid solution positive electrode, its mean particle size D in the embodiment of the present invention 250=8.5 μm, K90=
0.75, tap density is 2.23g/cm3。
Embodiment 3
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its preparation method comprises the following steps：
Step a3, according to rich lithium manganese base solid solution positive electrode chemical general formula 0.2Li2MnO3·0.8LiNi1/3Co1/3Mn1/ 3O2In manganese, nickel, cobalt mol ratio, manganese sulfate, nickel sulfate, cobaltous sulfate are mixed, being configured to metal ion total concentration is
2.5mol/L metal mixed salt solution.
Step b3, deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had stirring
The blade of oar, then under 600rpm speed of agitator, by the carbonic acid that the metal mixed salt solution and concentration are 1.5mol/L
Sodium solution continues cocurrent and is added in reactor, controls the metal mixed salt solution and the sodium carbonate liquor to add stream respectively
Speed, the pH value for making reaction solution is 8.1~8.2, and controlling reaction temperature is 45 DEG C, the reaction time is 30h, so as to be made lithium-rich manganese-based
The presoma slurries of solid solution cathode material.
Step c3, the presoma slurries to rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to separation of solid and liquid
Obtained solid is cleaned, and 8h is then dried at 120 DEG C, is sieved after 400 mesh sieves, so as to obtain presoma.
Step d3, according to Mn, Ni, Co three summation and Li mol ratio it is 1:1.2 ratio, by the presoma and hydrogen
Lithia is uniformly mixed, and in air atmosphere with 880 DEG C of sintering 15h, then Temperature fall and crush, cross 400 mesh sieves after crushing
Sieved, so that rich lithium manganese base solid solution positive electrode 0.2Li is made2MnO3·0.8LiNi1/3Co1/3Mn1/3O2。
Specifically, rich lithium manganese base solid solution positive electrode made from the step d3 of the embodiment of the present invention 3 is detected, can
To draw obtained rich lithium manganese base solid solution positive electrode, its mean particle size D in the embodiment of the present invention 350=10.4 μm, K90=
0.78, tap density is 2.31g/cm3。
Embodiment 4
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its preparation method comprises the following steps：
Step a4, according to rich lithium manganese base solid solution positive electrode chemical general formula 0.4Li2MnO3·
0.6LiNi0.6Co0.2Mn0.2O2In manganese, nickel, cobalt mol ratio, manganese acetate, nickel acetate, cobalt acetate are mixed, are configured to
Metal ion total concentration is 0.5mol/L metal mixed salt solution.
Step b4, deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had stirring
The blade of oar, then under 1000rpm speed of agitator, by the carbonic acid that the metal mixed salt solution and concentration are 1.5mol/L
Sodium solution continues cocurrent and is added in reactor, controls the metal mixed salt solution and the sodium carbonate liquor to add stream respectively
Speed, the pH value for making reaction solution is 7.8~7.9, and controlling reaction temperature is 35 DEG C, the reaction time is 12h, so as to be made lithium-rich manganese-based
The presoma slurries of solid solution cathode material.
Step c4, the presoma slurries to the rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to solid-liquid
Isolated solid is cleaned, and 20h is then dried at 100 DEG C, is sieved after 500 mesh sieves, so as to obtain forerunner
Body.
Step d4, according to Mn, Ni, Co three summation and Li mol ratio it is 1:1.4 ratio, by the presoma and hydrogen
Lithia is uniformly mixed, and in air atmosphere with 800 DEG C of sintering 12h, then Temperature fall and crush, cross 400 mesh sieves after crushing
Sieved, so that rich lithium manganese base solid solution positive electrode 0.4Li is made2MnO3·0.6LiNi0.6Co0.2Mn0.2O2。
Specifically, rich lithium manganese base solid solution positive electrode made from the step d4 of the embodiment of the present invention 4 is detected, can
To draw obtained rich lithium manganese base solid solution positive electrode, its mean particle size D in the embodiment of the present invention 450=4.6 μm, K90=
0.85, tap density is 2.06g/cm3。
Embodiment 5
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its preparation method comprises the following steps：
Step a5, according to rich lithium manganese base solid solution positive electrode chemical general formula 0.5Li2MnO3·
0.5LiNi0.4Co0.2Mn0.4O2In manganese, nickel, cobalt mol ratio, manganese nitrate, nickel nitrate, cobalt nitrate are mixed, are configured to
Metal ion total concentration is 1.5mol/L metal mixed salt solution.
Step b5, deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had stirring
The blade of oar, then under 900rpm speed of agitator, by the carbonic acid that the metal mixed salt solution and concentration are 2.5mol/L
Sodium solution continues cocurrent and is added in reactor, controls the metal mixed salt solution and the sodium carbonate liquor to add stream respectively
Speed, the pH value for making reaction solution is 8.0~8.1, and controlling reaction temperature is 40 DEG C, the reaction time is 20h, so as to be made lithium-rich manganese-based
The presoma slurries of solid solution cathode material.
Step c5, the presoma slurries to rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to separation of solid and liquid
Obtained solid is cleaned, and 2h is then dried at 150 DEG C, is sieved after 300 mesh sieves, so as to obtain presoma.
Step d5, according to Mn, Ni, Co three summation and Li mol ratio it is 1:1.5 ratio, by the presoma and carbon
Sour lithium is uniformly mixed, and in air atmosphere with 830 DEG C of sintering 14h, then Temperature fall and is crushed, it is broken after cross 300 mesh sieves and enter
Row screening, so that rich lithium manganese base solid solution positive electrode 0.5Li is made2MnO3·0.5LiNi0.4Co0.2Mn0.4O2。
Specifically, rich lithium manganese base solid solution positive electrode made from the step d5 of the embodiment of the present invention 5 is detected, can
To draw obtained rich lithium manganese base solid solution positive electrode, its mean particle size D in the embodiment of the present invention 550=6.9 μm, K90=
0.80, tap density is 2.22g/cm3。
Embodiment 6
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its preparation method comprises the following steps：
Step a6, by rich lithium manganese base solid solution positive electrode chemical general formula 0.25Li2MnO3·0.75LiNi1/3Co1/3Mn1/ 3O2In manganese, nickel, cobalt mol ratio, manganese chloride, nickel chloride, cobalt chloride are mixed, being configured to metal ion total concentration is
2mol/L metal mixed salt solution.
Step b6, deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had stirring
The blade of oar, then under 500rpm speed of agitator, by the sodium carbonate that the metal mixed salt solution and concentration are 2mol/L
Solution continues cocurrent and is added in reactor, controls the metal mixed salt solution and the sodium carbonate liquor to add stream respectively
Speed, the pH value for making reaction solution is 7.7~7.8, and controlling reaction temperature is 40 DEG C, the reaction time is 60h, so as to be made lithium-rich manganese-based
The presoma slurries of solid solution cathode material.
Step c6, the presoma slurries to rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to separation of solid and liquid
Obtained solid is cleaned, and 6h is then dried at 110 DEG C, is sieved after 300 mesh sieves, so as to obtain presoma.
Step d6, according to Mn, Ni, Co three summation and Li mol ratio it is 1:1.25 ratio, by the presoma with
Lithium carbonate is uniformly mixed, and with 890 DEG C of sintering 10h, then Temperature fall and is crushed, it is broken after cross 300 mesh sieves and sieved so that
Rich lithium manganese base solid solution positive electrode 0.25Li is made2MnO3·0.75LiNi1/3Co1/3Mn1/3O2。
Specifically, rich lithium manganese base solid solution positive electrode made from the step d6 of the embodiment of the present invention 6 is detected, can
To draw obtained rich lithium manganese base solid solution positive electrode, its mean particle size D in the embodiment of the present invention 650=14.6 μm, K90=
0.87, tap density is 2.49g/cm3。
Embodiment 7
A kind of lithium ion battery rich lithium manganese base solid solution positive electrode, its preparation method comprises the following steps：
Step a7, according to rich lithium manganese base solid solution positive electrode chemical general formula 0.7Li2MnO3·
0.3LiNi0.7Co0.2Mn0.1O2In manganese, nickel, cobalt mol ratio, manganese chloride, nickel chloride, cobalt chloride are mixed, are configured to
Metal ion total concentration is 3mol/L metal mixed salt solution.
Step b7, deionized water is added in the reactor with agitating paddle, the ionized water in reactor was not had stirring
The blade of oar, then under 600rpm speed of agitator, by the carbonic acid that the metal mixed salt solution and concentration are 1.0mol/L
Sodium solution continues cocurrent and is added in reactor, controls the metal mixed salt solution and the sodium carbonate liquor to add stream respectively
Speed, the pH value for making reaction solution is 8.2~8.3, and controlling reaction temperature is 45 DEG C, the reaction time is 40h, so as to be made lithium-rich manganese-based
The presoma slurries of solid solution cathode material.
Step c7, the presoma slurries to rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and to separation of solid and liquid
Obtained solid is cleaned, and 6h is then dried at 120 DEG C, is sieved after 300 mesh sieves, so as to obtain presoma.
Step d7, according to Mn, Ni, Co three summation and Li mol ratio it is 1:1.7 ratio, by the presoma and carbon
Sour lithium is uniformly mixed, and in air atmosphere with 850 DEG C of sintering 16h, then Temperature fall and is crushed, it is broken after cross 300 mesh sieves and enter
Row screening, so that rich lithium manganese base solid solution positive electrode 0.7Li is made2MnO3·0.3LiNi0.7Co0.2Mn0.1O2。
Specifically, rich lithium manganese base solid solution positive electrode made from the step d7 of the embodiment of the present invention 7 is detected, can
To draw obtained rich lithium manganese base solid solution positive electrode, its mean particle size D in the embodiment of the present invention 750=11.8 μm, K90=
0.76, tap density is 2.38g/cm3。
As fully visible, the lithium ion battery in the embodiment of the present invention with rich lithium manganese base solid solution anode material spherical degree it is good,
Closely knit, particle size distribution is narrow inside particle, so that the chemical property such as its capacity, cycle life can significantly improve.
And the lithium ion battery in the embodiment of the present invention with the preparation method of rich lithium manganese base solid solution positive electrode not only without using network
Mixture, and preparation technology is simple, the easy stability contorting of process, production cost are low, environment friendly and pollution-free, is adapted to heavy industrialization
Production.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (9)
1. a kind of lithium ion battery rich lithium manganese base solid solution positive electrode, it is characterised in that its chemical general formula is：
xLi2MnO3·(1-x)LiNiaCobMncO2, wherein 0.2≤x≤0.7, a+b+c=1,0.2≤a≤0.8,0.1≤c≤0.5；
Closely knit, tap density TD inside the particle of the rich lithium manganese base solid solution positive electrode>2.0g/cm3, size distribution COEFFICIENT K90For
0.6~0.9, wherein K90=(D90-D10)/D50。
2. lithium ion battery according to claim 1 rich lithium manganese base solid solution positive electrode, it is characterised in that described
The mean particle size D of rich lithium manganese base solid solution positive electrode50For 4 μm~15 μm.
3. a kind of lithium ion battery preparation method of rich lithium manganese base solid solution positive electrode, it is characterised in that including following step
Suddenly：
Step A, the chemical general formula xLi according to rich lithium manganese base solid solution positive electrode2MnO3·(1-x)LiNiaCobMncO2In
Manganese, nickel, cobalt mol ratio, manganese salt, nickel salt, cobalt salt are mixed, and it is 0.5~3mol/L's to be configured to metal ion total concentration
Metal mixed salt solution；Wherein, 0.2≤x≤0.7, a+b+c=1,0.2≤a≤0.8,0.1≤c≤0.5；
Step B, while stirring by the metal mixed salt solution and concentration for 0.5~2.5mol/L carbonate solution simultaneously
Stream is added in reactor, and the pH value for making reaction solution is 7.5~8.5, and controlling reaction temperature is 35~60 DEG C, the reaction time is 6
~60h, so that the presoma slurries of rich lithium manganese base solid solution positive electrode are made；
Step C, the presoma slurries to the rich lithium manganese base solid solution positive electrode carry out separation of solid and liquid, and separation of solid and liquid are obtained
To solid cleaned and dried, then cross 300~500 mesh sieves sieved, so as to obtain presoma；
Step D, the chemical general formula xLi according to rich lithium manganese base solid solution positive electrode2MnO3·(1-x)LiNiaCobMncO2Middle lithium
With manganese, nickel, cobalt mol ratio, the presoma is uniformly mixed with lithium source, and at 780~950 DEG C sinter 6~25h, then
Crushed and sieved, so that the lithium-rich manganese-based solid solution of lithium ion battery any one of the claims 1 to 2 is made
Body positive electrode.
4. the lithium ion battery according to claim 3 preparation method of rich lithium manganese base solid solution positive electrode, its feature
Be, in stepb, it is described while stirring by carbon that the metal mixed salt solution and concentration are 0.5~2.5mol/L
Acid salt solution cocurrent, which is added to reactor, to be included：Deionized water is added in the reactor with agitating paddle, is made in reactor
Ionized water do not had the blade of agitating paddle, then under 500~1000rpm speed of agitator, by the metal mixed salt solution
Be added to concentration for 0.5~2.5mol/L carbonate solution cocurrent in reactor, control the metal mixed salt solution and
The carbonate solution adds flow velocity, and the pH value for making reaction solution is 7.5~8.5.
5. the preparation method of the lithium ion battery rich lithium manganese base solid solution positive electrode according to claim 3 or 4, it is special
Levy and be, in step C, it is described the solid that separation of solid and liquid is obtained is cleaned and dried including：Separation of solid and liquid is obtained
Solid cleaned, then at 100~150 DEG C dry 2~20h.
6. the preparation method of the lithium ion battery rich lithium manganese base solid solution positive electrode according to claim 3 or 4, it is special
Levy and be, in step, the anion of the metal mixed salt solution is sulfate ion, salt acid ion, nitrate anion from
At least one of son, acetate ion.
7. the preparation method of the lithium ion battery rich lithium manganese base solid solution positive electrode according to claim 3 or 4, it is special
Levy and be, in stepb, the reaction time is 12~48h.
8. the preparation method of the lithium ion battery rich lithium manganese base solid solution positive electrode according to claim 3 or 4, it is special
Levy and be, in stepb, the carbonate solution is Na2CO3、K2CO3At least one of.
9. the preparation method of the lithium ion battery rich lithium manganese base solid solution positive electrode according to claim 3 or 4, it is special
Levy and be, in step E, the lithium source is Li2CO3, at least one of LiOH.
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