CN104218239B - Preparation method for lithium nickel-cobalt manganate cathode material - Google Patents
Preparation method for lithium nickel-cobalt manganate cathode material Download PDFInfo
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- CN104218239B CN104218239B CN201410415318.6A CN201410415318A CN104218239B CN 104218239 B CN104218239 B CN 104218239B CN 201410415318 A CN201410415318 A CN 201410415318A CN 104218239 B CN104218239 B CN 104218239B
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- sintering
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- salt
- cobalt
- cathode material
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- 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 title claims abstract description 37
- 239000010406 cathode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 58
- 238000005245 sintering Methods 0.000 claims abstract description 55
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002243 precursor Substances 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract 2
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000001556 precipitation Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- -1 ammonia radical ion Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 1
- PPPKZBCCLMQHSN-UHFFFAOYSA-N [Co++].[Ni++].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O Chemical compound [Co++].[Ni++].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O PPPKZBCCLMQHSN-UHFFFAOYSA-N 0.000 description 1
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing 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
- H01M4/48—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
- 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
- H01M4/52—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for lithium nickel-cobalt manganate cathode anode material, belonging to the field of cathode materials for lithium ion batteries. The method comprises the following steps: preparing a water solution of a mixture of a lithium salt, a nickel salt, a cobalt salt and a manganese salt according to a stoichiometric ratio of chemical formula LiNixCoyMnzO2, wherein in the chemical formula LiNixCoyMnzO2, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and the sum of x, y and z is 1; dropwise adding the water solution of the mixture into (NH4)2CO3 water solution under an agitating condition to obtain a mixed solution containing sediment; carrying out evaporation treatment on the mixed solution containing the sediment at 60-80 DEG C to remove water in the solution to obtain a precursor containing Li, Ni, Co and Mn; grinding the precursor; and carrying out two times of sintering treatment on the grinded precursor to obtain the lithium nickel-cobalt manganate cathode material. The method does not use clean water to wash so that wastewater is not generated and the loss of Li, Ni, Co and Mn ions is avoided.
Description
Technical field
The present invention relates to field of lithium ion battery anode, particularly to a kind of preparation of nickel-cobalt lithium manganate cathode material
Method.
Background technology
Lithium ion battery, as a kind of high-energy battery, has energy density height, long service life, good cycle and nothing
The advantages of memory effect, it is widely used in the electronic equipments such as mobile phone, digital camera.Anode material for lithium-ion batteries is lithium-ion electric
Important component part in pond, it has important impact for the chemical property of lithium ion battery.Commercial lithium ion at present
In cell positive material, the cobalt acid lithium market share is larger, but because cobalt resource is rare, expensive and poor safety performance, toxicity
Greatly, have a strong impact on and constrain the development of lithium ion battery.And nickle cobalt lithium manganate (LiNixCoyMnzO2, wherein, 0≤x≤1,0
≤ y≤1,0≤z≤1, x+y+z=1) it is a kind of anode material for lithium-ion batteries of excellent electrochemical performance, prepared using it
Lithium ion battery has the advantages that height ratio capacity, high-energy-density, self discharge be little, memory-less effect and cyclical stability are strong.
Generally nickel-cobalt lithium manganate cathode material is prepared using high temperature solid-state method and coprecipitation at present.With high temperature solid-state method
Compare, coprecipitation can make each material reach the mixing in molecule or atomic level it is easy to obtain that particle diameter is little, mix homogeneously
Positive electrode.Coprecipitation is mainly passed through to prepare the mixed solution of certain density nickel salt, cobalt salt and manganese salt, in certain pH ring
In border, so that this mixed solution is reacted with certain density sodium hydroxide solution, in this reaction system, then add ammonia radical ion
Obtain the precursor of nickel-cobalt-manganese ternary material, finally using a large amount of clear water wash gained precursor, remove impurity and make its
Effectively coordinated with lithium salts in sintering process, and this presoma after washing is sintered at high temperature with lithium salts, you can obtained
Nickel-cobalt lithium manganate cathode material.
For example, CN1622371A discloses and a kind of prepares nickel-cobalt lithium manganate cathode material using chemical coprecipitation
Method, step is as follows：Nickel salt, cobalt salt and manganese salt and sodium hydroxide, ammonia are reacted in aqueous, controls the pH of reaction system
For 10-12, synthesizing spherical or spherical hydroxide Ni1/3Co1/3Mn1/3(OH)2Precursor, is repeatedly washed before this using clear water
Drive body, mix with lithium carbonate after being dried, in atmosphere through sintering 8-48 hour under 750-950 DEG C of high temperature, obtain spherical nickel-cobalt
Manganate cathode material for lithium.
Inventor finds that prior art at least has problems with：
Prior art repeatedly washs presoma using clear water, not only produces a large amount of waste water, and is easily caused nickel, cobalt and manganese etc.
The loss of metal ion.
Content of the invention
Embodiment of the present invention technical problem to be solved is, there is provided one kind does not produce waste water, and metal ion is not
The preparation method of the nickel-cobalt lithium manganate cathode material being easy to run off.Concrete technical scheme is as follows：
Embodiments provide a kind of preparation method of nickel-cobalt lithium manganate cathode material, including：
Step a, according to chemical formula LiNixCoyMnzO2Stoichiometric proportion, prepare lithium salts, nickel salt, cobalt salt and manganese salt mixed
The aqueous solution of compound, wherein, described chemical formula LiNixCoyMnzO2In, 0≤x≤1,0≤y≤1,0≤z≤1, x+y+z=1；
Step b, under agitation, the aqueous solution of described mixture is added dropwise over (NH4)2CO3Aqueous solution in, obtain
To containing sedimentary mixed solution；
Step c, at 60-80 DEG C, carry out being evaporated process to described containing sedimentary mixed solution, contain described in removing
Moisture in sedimentary mixed solution, obtains the presoma containing Li, Ni, Co and Mn；
Step d, described presoma is ground process, then the presoma after milled processed is carried out at two-step sintering
Reason, obtains nickel-cobalt lithium manganate cathode material.
Specifically, in described step a, described lithium salts is LiNO3And/or CH3COOLi.
Specifically, in described step a, described nickel salt is Ni (NO3)2And/or Ni (CH3COO)2.
Specifically, in described step a, described cobalt salt is Co (NO3)2And/or Co (CH3COO)2.
Specifically, in described step a, described manganese salt is Mn (NO3)2And/or Mn (CH3COO)2.
Preferably, in described step b, in described mixture the integral molar quantity of lithium salts, nickel salt, cobalt salt and manganese salt with described
(NH4)2CO3Aqueous solution in (NH4)2CO3Mole ratio be 1：1-1.1.
Preferably, in described step c, by being placed in described in water-bath containing sedimentary mixed solution, using water
Bath heating carries out being evaporated process.
Specifically, the described temperature being evaporated process is 60 DEG C.
Specifically, in described step d, described two-step sintering processes and includes the first sintering processes and the second sintering processes；
The heating rate of described first sintering processes is 2-10 DEG C/min, and sintering temperature is 450-700 DEG C, and sintering time is
5-10h；
The heating rate of described second sintering processes is 2-10 DEG C/min, and sintering temperature is 700-1000 DEG C, sintering time
For 12-24h.
Preferably, the heating rate of described first sintering processes is 2 DEG C/min, and sintering temperature is 450 DEG C, and sintering time is
10h；
The heating rate of described second sintering processes is 2 DEG C/min, and sintering temperature is 700 DEG C, and sintering time is 24h.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
The preparation method of nickel-cobalt lithium manganate cathode material provided in an embodiment of the present invention, by make lithium salts, nickel salt, cobalt salt and
The aqueous solution of the mixture of manganese salt is added dropwise over (NH4)2CO3Aqueous solution in, make Li ion simultaneously straight with Ni, Co and Mn ion
Connect and equably precipitate completely, form spherical precipitation；Do not need to wash using clear water, by entering to the mixed solution containing this precipitation
Row is evaporated, and removes containing the moisture in reaction system, obtains the presoma of Li, Ni, Co and Mn, not only avoid the generation of waste water,
And avoid the loss of Li, Ni, Co and Mn ion；By two-step sintering is carried out to the presoma after grinding, before effectively removes
Drive NH present in body4+And other impurities, prepare the good nickel-cobalt lithium manganate cathode material of chemical property.
Brief description
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, will make to required in embodiment description below
Accompanying drawing be briefly described it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the XRD test chart of this nickel-cobalt lithium manganate cathode material that the embodiment of the present invention 1 provides；
Specific embodiment
For making technical scheme and advantage clearer, below in conjunction with accompanying drawing embodiment of the present invention is made into
One step ground describes in detail.
Embodiments provide a kind of preparation method of nickel-cobalt lithium manganate cathode material, including：
Step 101, according to chemical formula LiNixCoyMnzO2Stoichiometric proportion, prepare lithium salts, nickel salt, cobalt salt and manganese salt
The aqueous solution of mixture, wherein, described chemical formula LiNixCoyMnzO2In, 0≤x≤1,0≤y≤1,0≤z≤1, x+y+z=
1.
In step 101, lithium salts is LiNO3And/or CH3COOLi, nickel salt is Ni (NO3)2And/or Ni (CH3COO)2, cobalt salt
For Co (NO3)2And/or Co (CH3COO)2, manganese salt is Mn (NO3)2And/or Mn (CH3COO)2.In preparation process, can control
Lithium salts excess 1-2%, to compensate a small amount of volatilization at high temperature of the compound of lithium.
Step 102, under agitation, the aqueous solution of said mixture is added dropwise over (NH4)2CO3Aqueous solution in,
Obtain containing sedimentary mixed solution.
In step 102, by (NH4)2CO3It is suitable that material provides for reaction system, and is easy to the alkaline environment controlling,
To make lithium, nickel, cobalt and manganese ion precipitation.Preferably, the pH value of this alkaline environment is between 10-12.
Under above-mentioned suitable pH environment, under agitation, by being added dropwise over the aqueous solution of said mixture
(NH4)2CO3Aqueous solution in it is ensured that the controllability of course of reaction and uniformity, and avoid introducing unnecessary impurity.Specifically
Ground, in order that precipitation is evenly and completely, control mixing speed is 100-150rpm.
Further, in order that the precipitation uniform, controllable of above-mentioned each slaine and completely, control the above-mentioned speed being added dropwise over
Spend for 1-2 drop/sec.Wherein, in order to not increase (NH in reaction system4)2CO3Amount, in order to avoid producing unnecessary impurity, described
The integral molar quantity of lithium salts, nickel salt, cobalt salt and manganese salt and described (NH in mixture4)2CO3Aqueous solution in (NH4)2CO3Mole
The ratio of amount is 1：1-1.1.
It is understood that due to during being subsequently evaporated, needing to remove the moisture in reaction system, so, on
State the concentration of the aqueous solution of each material so that each raw material is completely dissolved, and can keep streamlined under gravity and dirty be advisable.
Step 103, at 60-80 DEG C, carry out being evaporated process to described containing sedimentary mixed solution, contain described in removing
There is the moisture in sedimentary mixed solution, obtain the presoma of Li, Ni, Co and Mn.
It is evaporated process for the ease of controlling, the embodiment of the present invention will be by being placed in water-bath containing sedimentary mixed solution
In, carry out being evaporated process using heating in water bath.Further, in order that the moisture containing in sedimentary mixed solution can be equal
Remove evenly, and make precipitate obtain enough digestion times, can carry out being evaporated place using heating in water bath under agitation
Reason.In order to prevent precipitate from decomposing in this mixed solution, in the embodiment of the present invention, the temperature that control is evaporated process is
60-80℃.
Step 104, described presoma is ground process, then two-step sintering is carried out to the presoma after milled processed
Process, obtain nickel-cobalt lithium manganate cathode material.
In order that presoma forms nickel-cobalt lithium manganate cathode material, and remove the impurity adulterating in this presoma, the present invention
Embodiment carries out two-step sintering process to this presoma, i.e. the first sintering processes and the second sintering processes；
Wherein, the heating rate of the first sintering processes is 2-10 DEG C/min, and sintering temperature is 450-700 DEG C, sintering time
For 5-10h；
The heating rate of the second sintering processes is 2-10 DEG C/min, and sintering temperature is 700-1000 DEG C, and sintering time is 12-
24h.
In order to improve the specific discharge capacity of formed nickel-cobalt lithium manganate cathode material, the intensification of the preferably first sintering processes
Speed is 2 DEG C/min, and sintering temperature is 450 DEG C, and sintering time is 10h, and the heating rate of the second sintering processes is 2 DEG C/min,
Sintering temperature is 700 DEG C, and sintering time is 24h.
In sum, the preparation method of nickel-cobalt lithium manganate cathode material provided in an embodiment of the present invention, by lithium salts, nickel
The aqueous solution of the mixture of salt, cobalt salt and manganese salt is added dropwise over (NH4)2CO3Aqueous solution in, make Li ion simultaneously with Ni, Co and
Mn ion Direct Uniform ground precipitation is completely.Because lithium ion is successfully combined uniformly in the process with other metal ions, no
Need to wash precipitation using clear water；By being evaporated to the mixed solution containing this precipitation, remove and contain sedimentary mixing
Moisture in solution, must have the presoma of Li, Ni, Co and Mn, not only avoid waste water and produce, and avoid Li, Ni, Co and Mn
The loss of ion；By two-step sintering is carried out to the presoma after grinding, effectively removes NH present in presoma4+And other
Impurity, prepares the good nickel-cobalt lithium manganate cathode material of chemical property.
It can be seen that, method provided in an embodiment of the present invention, due to avoiding using substantial amounts of water, on the one hand decreases energy consumption, profit
In increasing economic efficiency；On the other hand, therefore avoid a large amount of waste water of generation, reduce further energy consumption.By the side being evaporated
Formula removes contained moisture in reaction system, it is to avoid the losing issue of each metal ion in raw material, for improving prepared
The chemical property of nickel-cobalt lithium manganate cathode material have great importance.The method is simple, and easy to control, energy consumption is low, is easy to
Large-scale industrial is applied.
Hereinafter the present invention will be further described through by specific embodiment.
Embodiment 1
By lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate according to mol ratio 3.3:1:1:It is made into mixing in 1 addition distilled water
Solution, under the mixing speed of 130rpm, it is 30% that the above-mentioned mixed solution containing each metal ion is added dropwise over concentration
(NH4)2CO3Aqueous solution in, generate precipitation, obtain containing sedimentary mixed solution.This is contained sedimentary mixed solution
It is placed in water-bath, carries out heating in water bath under conditions of 60 DEG C, it is carried out being evaporated process, be somebody's turn to do containing sedimentary with removing
Moisture in mixed solution, obtains the precursor containing Li, Ni, Co, Mn.After the precursor obtaining is ground, with 2 DEG C/min liter
Warm speed, at a temperature of 450 DEG C, sinters 10h, then with 2 DEG C/min heating rate, sinters 24 at a temperature of 700 DEG C again
Hour, obtain solid product.This solid product is pulverized and grain size grading after obtain nickel-cobalt lithium manganate cathode material
LiNi1/3Co1/3Mn1/3O2.Using X-ray diffractometer, this nickel-cobalt lithium manganate cathode material is characterized, its XRD test chart is such as
It is seen then that LiNi obtained by the present embodiment shown in accompanying drawing 11/3Co1/3Mn1/3O2Li, Ni, Co, Mn are successfully combined by positive electrode.
Record this LiNi using FZS4-4 type tap density analyzer (purchased from Ningbo Ke Hai Shurui Instrument Ltd.)1/3Co1/3Mn1/ 3O2The tap density of positive electrode is 2.4g/cm3.It can be seen that, the density of the nickel-cobalt lithium manganate cathode material of present invention preparation is relatively
In prior art not too big change, maintain the stability of prior art nickel-cobalt lithium manganate cathode material.
Embodiment 2
By lithium acetate, nickel acetate, cobaltous acetate and manganese acetate according to mol ratio 3.3:1:1:It is made into mixing in 1 addition distilled water
Solution, under the mixing speed of 100rpm, it is 40% that the above-mentioned mixed solution containing each metal ion is added dropwise over concentration
(NH4)2CO3Aqueous solution in, generate precipitation, obtain containing sedimentary mixed solution.This is contained sedimentary mixed solution
It is placed in water-bath, carries out heating in water bath under conditions of 80 DEG C, it is carried out being evaporated process, be somebody's turn to do containing sedimentary with removing
Moisture in mixed solution, obtains the precursor containing Li, Ni, Co, Mn.After the precursor obtaining is ground, with 10 DEG C/min
Heating rate, at a temperature of 700 DEG C, sinters 5h, then with 10 DEG C/min heating rate, sinters again at a temperature of 1000 DEG C
12 hours, obtain solid product.This solid product is pulverized and grain size grading after obtain nickel-cobalt lithium manganate cathode material
LiNi1/3Co1/3Mn1/3O2.Record this LiNi using FZS4-4 type tap density analyzer1/3Co1/3Mn1/3O2The shaking of positive electrode
Real density is 2.3g/cm3.It can be seen that, the density of the nickel-cobalt lithium manganate cathode material of present invention preparation does not have with respect to prior art
Too big change, maintains the stability of prior art nickel-cobalt lithium manganate cathode material.
Embodiment 3
By lithium acetate, nickel acetate, cobaltous acetate and manganese acetate according to mol ratio 1.2:0.3:0.5:Join in 0.2 addition distilled water
Become mixed solution, under the mixing speed of 150rpm, the above-mentioned mixed solution containing each metal ion is added dropwise over concentration is
50% (NH4)2CO3Aqueous solution in, generate precipitation, obtain containing sedimentary mixed solution.This is contained sedimentary mixing
Close solution to be placed in water-bath, carry out heating in water bath under conditions of 70 DEG C, it is carried out being evaporated process, sunk with removing to contain
Moisture in the mixed solution of starch, obtains the precursor containing Li, Ni, Co, Mn.After the precursor obtaining is ground, with 6
DEG C/min heating rate, at a temperature of 550 DEG C, sinter 7h, then with 6 DEG C/min heating rate, at a temperature of 900 DEG C again
Sintering 16 hours, obtains solid product.This solid product is pulverized and grain size grading after obtain nickle cobalt lithium manganate positive pole
Material LiNi1/3Co1/3Mn1/3O2.Record this LiNi using FZS4-4 type tap density analyzer0.3Co0.5Mn0.2O2Positive electrode
Tap density be 2.5g/cm3.It can be seen that, the density of the nickel-cobalt lithium manganate cathode material of present invention preparation is with respect to prior art
Not too big change, maintains the stability of prior art nickel-cobalt lithium manganate cathode material.
Embodiment 4
By lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate according to mol ratio 1.1:0.4:0.3:Join in 0.3 addition distilled water
Become mixed solution, under the mixing speed of 120rpm, the above-mentioned mixed solution containing each metal ion is added dropwise over concentration is
25% (NH4)2CO3Aqueous solution in, generate precipitation, obtain containing sedimentary mixed solution.This is contained sedimentary mixing
Close solution to be placed in water-bath, carry out heating in water bath under conditions of 80 DEG C, it is carried out being evaporated process, sunk with removing to contain
Moisture in the mixed solution of starch, obtains the precursor containing Li, Ni, Co, Mn.After the precursor obtaining is ground, with 4
DEG C/min heating rate, at a temperature of 700 DEG C, sinter 5h, then with 4 DEG C/min heating rate, at a temperature of 800 DEG C again
Sintering 20 hours, obtains solid product.This solid product is pulverized and grain size grading after obtain nickle cobalt lithium manganate positive pole
Material LiNi1/3Co1/3Mn1/3O2.Record this LiNi using FZS4-4 type tap density analyzer0.4Co0.3Mn0.3O2Positive electrode
Tap density be 2.34g/cm3.It can be seen that, the density of the nickel-cobalt lithium manganate cathode material of present invention preparation is with respect to prior art
Not too big change, maintains the stability of prior art nickel-cobalt lithium manganate cathode material.
Embodiment 5
The present embodiment is utilized respectively the nickel-cobalt lithium manganate cathode material of embodiment 1-4 preparation preparing CR2025 type lithium ion
Button cell, and under conditions of charging and discharging currents are 0.1C, the charge-discharge performance of this lithium ion battery is tested.Its
In, the step preparing CR2025 type lithium-ion button battery is as follows：
Respectively by the nickel-cobalt lithium manganate material of embodiment 1-4 offer and conductive agent acetylene black, binding agent PVDF (polyvinylidene fluoride
Alkene) according to mass ratio 8：1：This mixture is modulated into slurry with NMP (1-Methyl-2-Pyrrolidone), uniformly by 1 mix homogeneously
It is coated on aluminium foil.Then this aluminium foil is put in baking oven, at 80 DEG C～120 DEG C, dry 1h, take out and be washed into pole piece.By this pole
Piece is vacuum dried 12 hours at 85 DEG C, carries out tabletting, is then vacuum dried 12 hours at 85 DEG C again, and prepared experimental cell is used
Pole piece.It is to electrode with lithium piece, electrolyte is the LiPF of 1.2mol/L6EC (ethyl carbonate ester)+DMC (dimethyl carbonate)
(volume ratio 1:1) solution, barrier film is celgard2400 film, is assembled into CR2025 type lithium in the glove box full of argon gas atmosphere
Ion button cell.And under conditions of charging and discharging currents are 0.1C, prepared each lithium-ion button battery is filled
Discharge performance is tested, and test result is as shown in table 1：
The charge-discharge performance test table of table 1 lithium-ion button battery
As shown in table 1, using the lithium ion battery prepared by nickel-cobalt lithium manganate cathode material provided in an embodiment of the present invention
There is excellent chemical property and good cyclical stability.It can be seen that, nickel is prepared by method provided in an embodiment of the present invention
Cobalt manganic acid lithium positive electrode not only avoid the substantial amounts of water of consumption, reducing energy consumption, and is beneficial to improve prepared nickle cobalt lithium manganate
The chemical property of positive electrode.The method is simple, easy to operate, is easy to large-scale industrial popularization and application.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the scope of the invention, all at this
Within bright spirit and principle, any modification, equivalent substitution and improvement made etc., should be included in protection scope of the present invention
Within.
Claims (9)
1. a kind of preparation method of nickel-cobalt lithium manganate cathode material, including：
Step a, according to chemical formula LiNixCoyMnzO2Stoichiometric proportion, prepare lithium salts, the mixture of nickel salt, cobalt salt and manganese salt
Aqueous solution, wherein, described chemical formula LiNixCoyMnzO2In, 0≤x≤1,0≤y≤1,0≤z≤1, x+y+z=1；
Step b, under agitation, control mixing speed is 100-150rmp, the aqueous solution of described mixture is dripped with 1-2/
The speed of second is added dropwise over (NH4)2CO3Aqueous solution in, obtain containing sedimentary mixed solution；
Lithium salts described in described mixture, the integral molar quantity of described nickel salt, described cobalt salt and described manganese salt and described (NH4)2CO3
Aqueous solution in (NH4)2CO3Mole ratio be 1：1-1.1；
Step c, at 60-80 DEG C, under agitation, carry out being evaporated process containing sedimentary mixed solution to described, remove
Remove the described moisture containing in sedimentary mixed solution, obtain the presoma containing Li, Ni, Co and Mn；
Step d, described presoma is ground process, then two-step sintering process is carried out to the presoma after milled processed,
Obtain nickel-cobalt lithium manganate cathode material.
2. method according to claim 1 is it is characterised in that in described step a, described lithium salts is LiNO3And/or
CH3COOLi.
3. method according to claim 1 is it is characterised in that in described step a, described nickel salt is Ni (NO3)2And/or Ni
(CH3COO)2.
4. method according to claim 1 is it is characterised in that in described step a, described cobalt salt is Co (NO3)2And/or Co
(CH3COO)2.
5. method according to claim 1 is it is characterised in that in described step a, described manganese salt is Mn (NO3)2And/or Mn
(CH3COO)2.
6. method according to claim 1 is it is characterised in that in described step c, by by described containing sedimentary mixed
Close solution to be placed in water-bath, carry out being evaporated process using heating in water bath.
7. method according to claim 6 is it is characterised in that the described temperature being evaporated process is 60 DEG C.
8. method according to claim 1 is it is characterised in that in described step d, described two-step sintering processes and includes first
Sintering processes and the second sintering processes；
The heating rate of described first sintering processes is 2-10 DEG C/min, and sintering temperature is 450-700 DEG C, and sintering time is 5-
10h；
The heating rate of described second sintering processes is 2-10 DEG C/min, and sintering temperature is 700-1000 DEG C, and sintering time is 12-
24h.
9. method according to claim 8 it is characterised in that described first sintering processes heating rate be 2 DEG C/min,
Sintering temperature is 450 DEG C, and sintering time is 10h；
The heating rate of described second sintering processes is 2 DEG C/min, and sintering temperature is 700 DEG C, and sintering time is 24h.
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| CN108545786A (en) * | 2018-03-22 | 2018-09-18 | 杭州金马新能源科技有限公司 | A kind of preparation method of high-energy nickel cobalt manganese compound lithium ion positive electrode |
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