CN107579236A - The preparation method of the complete nickelic ternary precursor of gradient and the nickelic tertiary cathode material of full gradient - Google Patents
The preparation method of the complete nickelic ternary precursor of gradient and the nickelic tertiary cathode material of full gradient Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 35
- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 130
- 238000005245 sintering Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 101
- 239000011572 manganese Substances 0.000 claims description 56
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 229910017052 cobalt Inorganic materials 0.000 claims description 35
- 239000010941 cobalt Substances 0.000 claims description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 35
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229910052748 manganese Inorganic materials 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 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 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 150000003839 salts Chemical class 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 28
- 238000005516 engineering process Methods 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011257 shell material Substances 0.000 description 5
- 229910015634 LiNi0.81 Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses the preparation method of the nickelic ternary precursor of full gradient and the nickelic tertiary cathode material of full gradient, comprise the steps of：Prepare mixed solution A, mixed solution B and mixed solution C, mixed solution A, alkaline solution and complexing agent cocurrent are pumped into reactor, after reaction time T1, mixed solution B is persistently pumped into mixed solution A with speed V1, after reaction time T2, mixed solution C is persistently pumped into mixed solution B with speed V2；Realize nickel salt, cobalt salt and the continuous alternation of manganese salt charging and composition, obtain the nickelic ternary precursor of full gradient, Li source compound and the nickelic ternary precursor of full gradient are mixed in molar ratio, obtained mixture is sintered under oxygen atmosphere, post-processed after sintering, obtain the nickelic tertiary cathode material of full gradient.Preparation method of the present invention is workable, easily controllable, and available for industrial production, products obtained therefrom capacity is high, good cycling stability.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, specifically, is related to the nickelic ternary forerunner of full gradient
The preparation method of body and the nickelic tertiary cathode material of full gradient.
Background technology
Energy crisis and energy security are the baptisms that our times various countries face, and improve energy resource structure, realize the energy
Diversification is the inevitable choice of national development.Lithium ion battery has high voltage, high-energy-density, good cycle, ring due to it
The advantage such as small is polluted in border, turns into an emphasis direction of various countries' New Energy Industry at present.And lithium ion anode material is
The important component of lithium ion battery, and the key point of performance of lithium ion battery.
Nickel-cobalt-manganternary ternary anode material is a kind of material for combining cobalt acid lithium, lithium nickelate and LiMn2O4 performance.Nickel cobalt manganese
Tertiary cathode material has the characteristics that height ratio capacity, long circulation life, low toxicity and cheap, has between three kinds of elements of nickel cobalt manganese good
Good cooperative effect, it is current most widely used material.Due to pursuit of the electric automobile to high-energy-density electrokinetic cell, pass
The nickel-cobalt-manganternary ternary anode material of system such as NMC111 types, NCM424 types, NCM523 types etc. can not meet to require, it is therefore desirable to compare
Capacity is higher, the bigger nickel-cobalt-manganternary ternary anode material of energy density.In redox energy storage, nickel is main component, is improved
The content of nickel can effectively improve the specific capacity of material in ternary material.Although nickelic system's tertiary cathode material, such as nickel cobalt
Material of the molar fraction of nickel more than 0.6 has height ratio capacity, cheap and advantages of environment protection in manganese ternary material,
But its poor cyclical stability, heat endurance and storge quality significantly limit its application.
In recent years, researchers have attempted a variety of methods, it is intended to which the nickelic ternary of get both height ratio capacity and high stability is just
Pole material.Conventional method has doping, coated but improvement degree of these work to material electrochemical performance is unsatisfactory.Remove
Outside above-mentioned modified method, the new technology and method of material preparation is also emerged frequently, such as by design of material into gradient core shell
The performance of material can be substantially improved in material, the nucleocapsid concentration gradient material prepared such as CN103236537A and CN102347483A
Material, but this functionally gradient material (FGM), nuclear material have obvious component difference with shell material, and multiple circulation can cause the stripping of shell material
Fall, lose effect, material property reduces；Design of material is helped into functionally gradient material (FGM), i.e., it is continuous from core to shell material concentration components
Change, without point of obvious shell core, can effectively solve this problem, but full functionally gradient material (FGM) prepares difficult, poor controllability,
The instrument and strict manipulation condition for needing precision are not easy industrialized production.Therefore urgently seek a kind of controllable, reproducible
Be easy to industrialized preparation method.
In view of this it is special to propose the present invention.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided the nickelic ternary precursor of full gradient
And the preparation method of the complete nickelic tertiary cathode material of gradient, solve full functionally gradient material (FGM) and be difficult to carry out the technology of industrialized production to ask
Topic.
In order to solve the above technical problems, the present invention is using the basic conception of technical scheme：
The preparation method of the nickelic ternary precursor of full gradient, comprises the following steps：
S1：Prepare mixed solution A, mixed solution B and mixed solution C；
S2：Reacted in reactor：Mixed solution A, alkaline solution and complexing agent cocurrent are pumped into reactor, reacted
Be full of protective gas in kettle, it is 45~70 DEG C control the temperature in reactor, and the pH value in control reactor is opened 10~12.5
Agitating device in dynamic reactor, stirring reaction, after reaction time T1, it is molten that mixed solution B is persistently pumped into speed V1 to mixing
In liquid A, after reaction time T2, mixed solution C is persistently pumped into mixed solution B with speed V2；
S3：Stop reaction：After mixed solution A, mixed solution B, mixed solution C are pumped into reactor completely, stop alkali
Property solution and complexing agent be pumped into reactor, question response stops, obtaining reaction product；
S4：Product processing：Reaction product in reactor is aged, filter-press water-washing, drying, it is nickelic to obtain full gradient
Ternary precursor.
In the present invention, the method that mixed solution A, mixed solution B and mixed solution C are prepared in S1 is as follows：
Nickel salt, cobalt salt and manganese salt are added in deionized water, prepares mixed solution A, control mole of nickel in mixed solution A
The ratio between molar concentration of concentration, the molar concentration of cobalt and manganese is (1-x-y)：x：y；
Nickel salt, cobalt salt and manganese salt are added in deionized water, prepares mixed solution B, control mole of nickel in mixed solution B
The ratio between molar concentration of concentration, the molar concentration of cobalt and manganese is (1-a-b)：a：b；
Nickel salt, cobalt salt and manganese salt are added in deionized water, prepares mixed solution C, control mole of nickel in mixed solution C
The ratio between molar concentration of concentration, the molar concentration of cobalt and manganese is 1：1：1；
Wherein, 1/3 ＜ (1-a-b) ＜ (1-x-y).
In the present invention, nickel salt described in S1 be nickel sulfate, nickel chloride, nickel nitrate or nickel acetate in one kind, the cobalt salt
For one kind in cobaltous sulfate, cobalt chloride, cobalt nitrate or cobalt acetate, the manganese salt is manganese sulfate, manganese chloride, manganese nitrate or manganese acetate
In one kind, in S1,0≤x≤0.1,0≤y≤0.1；In S1,0.15≤a≤0.35,0.2≤b≤0.4.
In the present invention, in S1 control mixed solution A in the molar concentration of nickel, the molar concentration of cobalt and manganese molar concentration it
With for 1~4.5mol/L；The molar concentration sum for controlling the molar concentration of nickel, the molar concentration of cobalt and manganese in mixed solution B is
0.5~3.5mol/L；The molar concentration sum for controlling the molar concentration of nickel, the molar concentration of cobalt and manganese in mixed solution C is 0.5
~2.5mol/L.
In the present invention, mixed solution A is stored in the first head tank in S2, and mixed solution B is stored in the second head tank,
Mixed solution C is stored in the 3rd head tank, and stirring dress is provided with the first head tank, the second head tank and the 3rd head tank
Put, the second raw material pot bottom is connected by pipeline with the first head tank, on the pipeline of the second head tank and the connection of the first head tank
Measuring pump is installed, the 3rd raw material pot bottom is connected by pipeline with the second head tank, and the 3rd head tank and the second head tank connect
Measuring pump is installed on logical pipeline.
In the present invention, alkaline solution described in S2 is one of sodium hydroxide solution or potassium hydroxide solution, the alkalescence
The molar concentration of solution is 2~8mol/L, and complexing agent described in S2 is one of ammoniacal liquor or ammonium salt solution, and the complexing agent rubs
Your concentration is 2~8mol/L, and protective gas described in S2 is one of nitrogen or argon gas, the agitating device in S2 in reactor
Mixing speed is 300~800rpm/min, controls the device of the pH value in reactor to be counted for online PH in S2.
In the present invention, reaction time T1 is 0.5~5 hour in S2, and reaction time T2 is 2~12 hours, and speed V1 is 6L/
H~20L/h, speed V2 are 4L/h~12L/h.
The preparation method of the nickelic tertiary cathode material of full gradient, comprises the following steps：
S01：The nickelic ternary precursor of full gradient is prepared, is prepared according to the preparation method of the nickelic ternary precursor of full gradient complete
The nickelic ternary precursor of gradient；
S02：Mixing：Li source compound and the nickelic ternary precursor of full gradient are mixed in molar ratio；Obtain mixture；
S03：Sintering：Obtained mixture is sintered under oxygen atmosphere, is post-processed after sintering, obtains full ladder
Spend nickelic tertiary cathode material.
In the present invention, Li source compound described in S02 is one or two kinds of in lithium hydroxide, lithium carbonate, will in S02
Li source compound and the nickelic ternary precursor of full gradient are according to mol ratio Li:(Ni+Co+Mn)=1~1.1:1 mixing.
In the present invention, sintering two stages of experience in S03, first stage sintering temperature is controlled at 400~550 DEG C, sintering
Temperature-time control in 4~12h, the control of second stage sintering temperature at 650~900 DEG C, sintering temperature time control 10~
Post processing is carried out after being sintered in 25h, S03 as dissociation and sieving.
After adopting the above technical scheme, the present invention has the advantages that compared with prior art.
Ternary precursor technology of preparing provided by the invention changes the preparation technology and routine of conventional single salting liquid
Functionally gradient material (FGM) preparation technology, the mixed solution A of the high nickel content by preparing various concentrations, the mixing of the nickel cobalt manganese of middle nickel content
Solution B and nickel cobalt manganese mol ratio 1：1：1 solution mixing C, it is pumped into reactor the nickelic mixed liquor A of the stage of reaction is lasting
Reaction consumption, and middle nickel solution B is continual is pumped into solution A, solution C is again continual to be pumped into solution B, actually
Nickel content into the mixed liquor of reactor is gradually successively decreased, and cobalt, manganese content are gradually incremented by, and realize nickel salt, cobalt salt and manganese salt and enter
The continuous alternation of material and composition, to prepare the nickelic ternary precursor of full gradient, then it is calcined by mixed lithium and synthesizes full gradient height
Nickel tertiary cathode material.The material from core center to shell, constantly successively decrease by nickel content, and cobalt, manganese element content are constantly incremental,
Presoma preparatory phase by control different solutions feed time and flow ensure that material outermost layer be structure and electrically
The component and structure of the stable NCM111 of energy and material are in continuity graded, and material internal does not have obvious interface, reduces
Phase boundary resistance between material, optimize the performance of material.The preparation method of the present invention is workable, easily controllable, can
For industrial production, products obtained therefrom capacity is high, good cycling stability.
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Brief description of the drawings
A part of the accompanying drawing as the application, for providing further understanding of the invention, of the invention is schematic
Embodiment and its illustrate to be used to explain the present invention, but do not form inappropriate limitation of the present invention.Obviously, drawings in the following description
Only some embodiments, to those skilled in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.In the accompanying drawings：
It is the process flow diagram of the present invention shown in Fig. 1.
It should be noted that these accompanying drawings and word description are not intended as the design model limiting the invention in any way
Enclose, but be that those skilled in the art illustrate idea of the invention by reference to specific embodiment.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in embodiment is clearly and completely described, following examples be used for illustrate the present invention, but
It is not limited to the scope of the present invention.
It is term " on ", " under ", "front", "rear", "left", "right", " perpendicular in the description of the invention, it is necessary to explanation
Directly ", the orientation of the instruction such as " interior ", " outer " or position relationship are based on orientation shown in the drawings or position relationship, merely to just
In the description present invention and simplify description, rather than instruction or imply signified device or element must have specific orientation, with
Specific azimuth configuration and operation, therefore be not considered as limiting the invention.
In the description of the invention, it is necessary to illustrate, unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected, or be integrally connected；Can
To be mechanical connection or electrical connection；Can be joined directly together, can also be indirectly connected by intermediary.For this
For the those of ordinary skill in field, the concrete meaning of above-mentioned term in the present invention can be understood with concrete condition.
Embodiment 1
Referring to Fig. 1, the process flow diagram of the preparation method of the complete nickelic tertiary cathode material of gradient, in deionized water
Nickel sulfate, cobaltous sulfate are added, prepares 400L mixed solution A, controls the mole dense of the molar concentration of nickel and cobalt in mixed solution A
The ratio between degree is 0.95：0.05, it is 3mol/L to control the molar concentration of nickel and the molar concentration sum of cobalt in mixed solution A；Will be mixed
Close solution A to be stored in the first head tank, start the agitating device set in the first head tank；Sulfuric acid is added in deionized water
Nickel, cobaltous sulfate, manganese sulfate, 200L mixed solution B is prepared, control molar concentration, the molar concentration of cobalt of nickel in mixed solution B
It is 5 with the ratio between the molar concentration of manganese：2：Mole of the molar concentration of nickel, the molar concentration of cobalt and manganese in 3, control mixed solution B
Concentration sum is 2mol/L；Mixed solution B is stored in the second head tank, starts the stirring dress set in the second head tank
Put；Nickel sulfate, cobaltous sulfate, manganese sulfate are added in deionized water, prepares 100L mixed solution C, control nickel in mixed solution C
Molar concentration, the ratio between the molar concentration of the molar concentration of cobalt and manganese be 1：1：1；Control mixed solution C in nickel molar concentration,
The molar concentration of cobalt and the molar concentration sum of manganese are 1mol/L, and mixed solution C is stored in the 3rd head tank, start the 3rd
The agitating device set in head tank；It is by sodium hydroxide solution and molar concentration that mixed solution A, molar concentration are 4mol/L
5mol/L ammoniacal liquor cocurrents are pumped into reactor, and nitrogen is full of in reactor, and it is 60 DEG C to control the temperature in reactor, control
Agitating device of the pH value in 11.5, startup reactor in reactor, the mixing speed of agitating device is 500rpm/min, is stirred
Mix reaction, after reaction time 2h, mixed solution B is persistently pumped into mixed solution A with speed 11L/h, after reaction time 10h,
Mixed solution C is persistently pumped into mixed solution B with speed 5L/h；When mixed solution A, mixed solution B, mixed solution C are complete
After being pumped into reactor entirely, it is that 5mol/L ammoniacal liquor is pumped into reactor to stop 4mol/L sodium hydroxide solution and molar concentration, is treated anti-
It should stop；Obtain reaction product；Because consumption is reacted in lasting being pumped into reactor of the mixed solution A of the first head tank, and the
The middle mixed solution B of two head tanks is persistently pumped into mixed liquor A with 11L/h speed, the mixed solution C of the 3rd head tank again with
5L/h speed is persistently pumped into mixed solution B, and the nickel content in actually the first head tank is gradually successively decreased, and cobalt manganese content is gradually passed
Increase, realize nickel salt, cobalt salt and the continuous alternation of manganese salt charging and composition；Reaction product in reactor is aged, pressed
Drainage is washed, dried, and obtains the nickelic ternary precursor Ni of full gradient0.81Co0.10Mn0.09(OH)2, by Li source compound and full gradient
Nickelic ternary precursor Ni0.81Co0.10Mn0.09(OH)2According to mol ratio Li:(Ni+Co+Mn)=1.03:1 mixing；Mixed
Thing；Obtained mixture is sintered under oxygen atmosphere, sintering two stages of experience, first stage sintering temperature control exists
500 DEG C, sintering temperature time control in 6h, the control of second stage sintering temperature at 795 DEG C, sintering temperature time control in 15h,
Dissociated and sieved after sintering, obtain the nickelic tertiary cathode material LiNi of full gradient0.81Co0.10Mn0.09O2。
Comparative example 1
Nickel sulfate, cobaltous sulfate, manganese sulfate are added in deionized water, prepares 700L mixed solution, control mixed solution
The ratio between molar concentration of the molar concentration of middle nickel, the molar concentration of cobalt and manganese is 0.81：0.1：0.09, control nickel in mixed solution
Molar concentration, the molar concentration sum of the molar concentration of cobalt and manganese be 3mol/L；By mixed solution, molar concentration 4mol/L
Sodium hydroxide solution and molar concentration be 5mol/L ammoniacal liquor cocurrents be pumped into reactor, nitrogen be full of in reactor, control
Temperature in reactor processed is 60 DEG C, controls agitating device of the pH value in 11.5, startup reactor in reactor, stirring dress
The mixing speed put is 500rpm/min, after mixed solution is pumped into reactor completely, stops 4mol/L sodium hydroxide solution
It is that 5mol/L ammoniacal liquor is pumped into reactor with molar concentration, question response stops；Obtain reaction product；By the reaction product in reactor
Be aged, filter-press water-washing, drying, obtain nickelic ternary precursor Ni0.81Co0.10Mn0.09(OH)2, by Li source compound and height
Nickel ternary precursor Ni0.81Co0.10Mn0.09(OH)2According to mol ratio Li:(Ni+Co+Mn)=1.03:1 mixing；Mixed
Thing；Obtained mixture is sintered under oxygen atmosphere, sintering two stages of experience, first stage sintering temperature control exists
500 DEG C, sintering temperature time control in 6h, the control of second stage sintering temperature at 795 DEG C, sintering temperature time control in 15h,
Dissociated and sieved after sintering, obtain nickelic tertiary cathode material LiNi0.81Co0.10Mn0.09O2。
The nickelic tertiary cathode material LiNi of full gradient prepared by embodiment 10.81Co0.10Mn0.09O2Prepared with comparative example 1
Nickelic tertiary cathode material LiNi0.81Co0.10Mn0.09O22032 button cells are respectively prepared, using blue electrical measurement test system 25
Tested at DEG C, test voltage 2.8~4.3V of scope, the nickelic tertiary cathode material of full gradient prepared by embodiment 1
LiNi0.81Co0.10Mn0.09O2Discharge capacity is 186.8mAh/g to the 1C of made 2032 button cell first；Battery 1000 times entirely
Battery capacity conservation rate is 93.8% after circulation, and nickelic tertiary cathode material prepared by comparative example 1
LiNi0.81Co0.10Mn0.09O2Discharge capacity is 183.7mAh/g to the 1C of made 2032 button cell first；Battery 1000 times entirely
Battery capacity conservation rate is 85.3% after circulation.Products obtained therefrom capacity of the present invention is higher, good cycling stability, and the present invention's is complete
The nickelic ternary precursor of gradient and method for preparing anode material are workable, easily controllable, available for industrial production.
Embodiment 2
Referring to Fig. 1, the process flow diagram of the preparation method of the complete nickelic tertiary cathode material of gradient, in deionized water
Nickel sulfate, cobaltous sulfate, manganese sulfate are added, prepares 300L mixed solution A, controls the molar concentration of nickel in mixed solution A, cobalt
The ratio between molar concentration and the molar concentration of manganese are 8：1：1, control mixed solution A in nickel molar concentration and cobalt molar concentration it
With for 2mol/L；Mixed solution A is stored in the first head tank, starts the agitating device set in the first head tank；Going
Nickel sulfate, cobaltous sulfate, manganese sulfate are added in ionized water, prepares 100L mixed solution B, controls mole of nickel in mixed solution B
The ratio between molar concentration of concentration, the molar concentration of cobalt and manganese is 6：2：The molar concentration of nickel in 2, control mixed solution B, cobalt rub
That concentration and the molar concentration sum of manganese are 1mol/L；Mixed solution B is stored in the second head tank, starts the second head tank
The agitating device of middle setting；Nickel sulfate, cobaltous sulfate, manganese sulfate are added in deionized water, prepare 100L mixed solution C, control
The ratio between molar concentration of the molar concentration of nickel, the molar concentration of cobalt and manganese is 1 in mixed solution C processed：1：1；Control mixed solution C
The molar concentration sum of the molar concentration of middle nickel, the molar concentration of cobalt and manganese is 1mol/L, and it is former that mixed solution C is stored in into the 3rd
In batch can, start the agitating device set in the 3rd head tank；By mixed solution A, the sodium hydroxide that molar concentration is 4mol/L
Solution and molar concentration are that 6mol/L ammoniacal liquor cocurrents are pumped into reactor, and nitrogen is full of in reactor, is controlled in reactor
Temperature be 60 DEG C, control the pH value in reactor 11.2, start the agitating device in reactor, the stirring speed of agitating device
Spend for 600rpm/min, stirring reaction, after reaction time 1.5h, mixed solution B is persistently pumped into mixed solution A with speed 8L/h
In, after reaction time 7.0h, mixed solution C is persistently pumped into mixed solution B with speed 5L/h；When mixed solution A, mixing are molten
After liquid B, mixed solution C are pumped into reactor completely, it is 6mol/L ammonia to stop 4mol/L sodium hydroxide solution and molar concentration
Water is pumped into reactor, and question response stops；Obtain reaction product；Due to the mixed solution A of the first head tank it is lasting be pumped into reaction
Consumption is reacted in kettle, and the middle mixed solution B of the second head tank is persistently pumped into mixed liquor A with 8L/h speed, the 3rd head tank
Mixed solution C again be persistently pumped into mixed solution B with 5L/h speed, the nickel content in actually the first head tank is gradually passed
Subtract, cobalt manganese content is gradually incremented by, and realizes nickel salt, cobalt salt and the continuous alternation of manganese salt charging and composition；Will be anti-in reactor
Answer product to be aged, filter-press water-washing, drying, obtain the nickelic ternary precursor Ni of full gradient0.72Co0.14Mn0.14(OH)2, by lithium
Source compound and the nickelic ternary precursor Ni of full gradient0.72Co0.14Mn0.14(OH)2According to mol ratio Li:(Ni+Co+Mn)=
1.05:1 mixing；Obtain mixture；Obtained mixture is sintered under oxygen atmosphere, sintering two stages of experience, the
At 500 DEG C, sintering temperature time control controls at 820 DEG C the control of one stage sintering temperature in 8h, second stage sintering temperature, burns
Junction temperature time control is dissociated and sieved after 16h, sintering, obtains the nickelic tertiary cathode material of full gradient
LiNi0.72Co0.14Mn0.14O2.The nickelic tertiary cathode material LiNi of full gradient prepared by embodiment 20.72Co0.14Mn0.14O2It is made
2032 button cells, tested using blue electrical measurement test system at 25 DEG C, test voltage 2.8~4.3V of scope, embodiment 2 is made
The nickelic tertiary cathode material LiNi of standby full gradient0.72Co0.14Mn0.14O2The 1C of made 2032 button cell discharges appearance first
Measure as 176.5mAh/g；Battery capacity conservation rate is 94.9% after complete 1000 circulations of battery.
Embodiment 3
Referring to Fig. 1, the process flow diagram of the preparation method of the complete nickelic tertiary cathode material of gradient, in deionized water
Nickel sulfate is added, prepares 300L mixed solution A, the molar concentration for controlling nickel in mixed solution A is 4mol/L；By mixed solution
A is stored in the first head tank, starts the agitating device set in the first head tank；Nickel sulfate, sulphur are added in deionized water
Sour cobalt, manganese sulfate, 100L mixed solution B is prepared, control the molar concentration of nickel, the molar concentration of cobalt and manganese in mixed solution B
The ratio between molar concentration be 4：2：The molar concentration of the molar concentration of nickel, the molar concentration of cobalt and manganese in 4, control mixed solution B
Sum is 2mol/L；Mixed solution B is stored in the second head tank, starts the agitating device set in the second head tank；
Nickel sulfate, cobaltous sulfate, manganese sulfate are added in deionized water, prepares 100L mixed solution C, controls rubbing for nickel in mixed solution C
The ratio between molar concentration of your concentration, the molar concentration of cobalt and manganese is 1：1：1；Control the molar concentration of nickel in mixed solution C, cobalt
Molar concentration and the molar concentration sum of manganese are 1mol/L, and mixed solution C is stored in the 3rd head tank, start the 3rd raw material
The agitating device set in tank；It is by sodium hydroxide solution and molar concentration that mixed solution A, molar concentration are 4mol/L
5mol/L ammoniacal liquor cocurrents are pumped into reactor, and nitrogen is full of in reactor, and it is 60 DEG C to control the temperature in reactor, control
Agitating device of the pH value in 11.6, startup reactor in reactor, the mixing speed of agitating device is 500rpm/min, is stirred
Mix reaction, after reaction time 1h, mixed solution B is persistently pumped into mixed solution A with speed 10L/h, will after reaction time 5h
Mixed solution C is persistently pumped into mixed solution B with speed 6L/h；When mixed solution A, mixed solution B, mixed solution C are complete
After being pumped into reactor, it is that 5mol/L ammoniacal liquor is pumped into reactor, question response to stop 4mol/L sodium hydroxide solution and molar concentration
Stop；Obtain reaction product；Because consumption is reacted in lasting being pumped into reactor of the mixed solution A of the first head tank, and second
The middle mixed solution B of head tank is persistently pumped into mixed liquor A with 10L/h speed, and the mixed solution C of the 3rd head tank is again with 6L/h
Speed is persistently pumped into mixed solution B, and the nickel content in actually the first head tank is gradually successively decreased, and cobalt manganese content is gradually incremented by,
Realize nickel salt, cobalt salt and the continuous alternation of manganese salt charging and composition；Reaction product in reactor is aged, press filtration water
Wash, dry, obtain the nickelic ternary precursor Ni of full gradient0.88Co0.05Mn0.07(OH)2, Li source compound and full gradient is nickelic
Ternary precursor Ni0.88Co0.05Mn0.07(OH)2According to mol ratio Li:(Ni+Co+Mn)=1.02:1 mixing；Obtain mixture；
Obtained mixture is sintered under oxygen atmosphere, in sintering two stages of experience, first stage sintering temperature is controlled 500
DEG C, sintering temperature time control is in 8h, and second stage sintering temperature is controlled at 750 DEG C, and sintering temperature time control is in 18h, burning
Dissociated and sieved after knot, obtain the nickelic tertiary cathode material LiNi of full gradient0.88Co0.05Mn0.07O2.It is prepared by embodiment 3
The nickelic tertiary cathode material LiNi of full gradient0.88Co0.05Mn0.07O22032 button cells are made, are existed using blue electrical measurement test system
Tested at 25 DEG C, test voltage 2.8~4.3V of scope, the nickelic tertiary cathode material of full gradient prepared by embodiment 3
LiNi0.88Co0.05Mn0.07O2Discharge capacity is 198.6mAh/g to the 1C of made 2032 button cell first；Battery 1000 times entirely
Battery capacity conservation rate is 92.5% after circulation.
Described above is only presently preferred embodiments of the present invention, not makees any formal limitation to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompting make it is a little change or be modified to
The equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit pair according to the present invention
Any simple modification, equivalent change and modification that above example is made, in the range of still falling within the present invention program.
Claims (10)
1. the preparation method of the complete nickelic ternary precursor of gradient, it is characterised in that comprise the following steps：
S1：Prepare mixed solution A, mixed solution B and mixed solution C；
S2：Reacted in reactor：Mixed solution A, alkaline solution and complexing agent cocurrent are pumped into reactor, in reactor
Full of protective gas, it is 45~70 DEG C to control the temperature in reactor, controls pH value in reactor to start anti-10~12.5
Answer the agitating device in kettle, stirring reaction, after reaction time T1, mixed solution B is persistently pumped into mixed solution A with speed V1
In, after reaction time T2, mixed solution C is persistently pumped into mixed solution B with speed V2；
S3：Stop reaction：After mixed solution A, mixed solution B, mixed solution C are pumped into reactor completely, it is molten to stop alkalescence
Liquid and complexing agent are pumped into reactor, and question response stops, and obtains reaction product；
S4：Product processing：Reaction product in reactor is aged, filter-press water-washing, drying, obtain the nickelic ternary of full gradient
Presoma.
2. the preparation method of the nickelic ternary precursor of full gradient according to claim 1, it is characterised in that prepared in S1 mixed
The method for closing solution A, mixed solution B and mixed solution C is as follows：
Nickel salt, cobalt salt and manganese salt are added in deionized water, prepares mixed solution A, control the mole dense of nickel in mixed solution A
The ratio between molar concentration of degree, the molar concentration of cobalt and manganese is (1-x-y)：x：y；
Nickel salt, cobalt salt and manganese salt are added in deionized water, prepares mixed solution B, and nickel is mole dense in control mixed solution B
The ratio between molar concentration of degree, the molar concentration of cobalt and manganese is (1-a-b)：a：b；
Nickel salt, cobalt salt and manganese salt are added in deionized water, prepares mixed solution C, control the mole dense of nickel in mixed solution C
The ratio between molar concentration of degree, the molar concentration of cobalt and manganese is 1：1：1；
Wherein, 1/3 ＜ (1-a-b) ＜ (1-x-y).
3. the preparation method of the nickelic ternary precursor of full gradient according to claim 1, it is characterised in that nickel described in S1
Salt is one kind in nickel sulfate, nickel chloride, nickel nitrate or nickel acetate, and the cobalt salt is cobaltous sulfate, cobalt chloride, cobalt nitrate or acetic acid
One kind in cobalt, the manganese salt is one kind in manganese sulfate, manganese chloride, manganese nitrate or manganese acetate, in S1,0≤x≤0.1,0≤y
≤0.1；In S1,0.15≤a≤0.35,0.2≤b≤0.4.
4. the preparation method of the nickelic ternary precursor of full gradient according to claim 1, it is characterised in that controlled in S1 mixed
The molar concentration sum for closing the molar concentration of nickel, the molar concentration of cobalt and manganese in solution A is 1~4.5mol/L；Control mixing is molten
The molar concentration sum of the molar concentration of nickel, the molar concentration of cobalt and manganese is 0.5~3.5mol/L in liquid B；Control mixed solution C
The molar concentration sum of the molar concentration of middle nickel, the molar concentration of cobalt and manganese is 0.5~2.5mol/L.
5. the preparation method of the nickelic ternary precursor of full gradient according to claim 1, it is characterised in that mixed in S2 molten
Liquid A is stored in the first head tank, and mixed solution B is stored in the second head tank, and mixed solution C is stored in the 3rd head tank
In, agitating device is provided with the first head tank, the second head tank and the 3rd head tank, the second raw material pot bottom passes through pipeline
Connected with the first head tank, measuring pump, the 3rd head tank bottom are installed on the pipeline of the second head tank and the connection of the first head tank
Portion is connected by pipeline with the second head tank, and measuring pump is provided with the pipeline of the 3rd head tank and the connection of the second head tank.
6. the preparation method of the nickelic ternary precursor of full gradient according to claim 1, it is characterised in that alkali described in S2
Property solution is one of sodium hydroxide solution or potassium hydroxide solution, and the molar concentration of the alkaline solution is 2~8mol/L, S2
Described in complexing agent be one of ammoniacal liquor or ammonium salt solution, the molar concentration of the complexing agent is 2~8mol/L, is protected described in S2
Shield gas is one of nitrogen or argon gas, and the mixing speed of the agitating device in S2 in reactor is 300~800rpm/min, S2
The middle device for controlling the pH value in reactor is counted for online PH.
7. the preparation method of the nickelic ternary precursor of full gradient according to claim 1, it is characterised in that when being reacted in S2
Between T1 be 0.5~5 hour, reaction time T2 be 2~12 hours, speed V1 is 6L/h~20L/h, and speed V2 is 4L/h~12L/
h。
8. the preparation method of the complete nickelic tertiary cathode material of gradient, it is characterised in that comprise the following steps：
S01：The nickelic ternary precursor of full gradient is prepared, full gradient is prepared according to the preparation method of the nickelic ternary precursor of full gradient
Nickelic ternary precursor；
S02：Mixing：Li source compound and the nickelic ternary precursor of full gradient are mixed in molar ratio；Obtain mixture；
S03：Sintering：Obtained mixture is sintered under oxygen atmosphere, post-processed after sintering, it is high to obtain full gradient
Nickel tertiary cathode material.
9. the preparation method of the nickelic tertiary cathode material of full gradient according to claim 8, it is characterised in that institute in S02
Li source compound is stated to be one or two kinds of in lithium hydroxide, lithium carbonate, by Li source compound and full gradient nickelic three in S02
First presoma is according to mol ratio Li:(Ni+Co+Mn)=1~1.1:1 mixing.
10. the preparation method of the nickelic tertiary cathode material of full gradient according to claim 8, it is characterised in that burnt in S03
Tying-in goes through two stages, and the control of first stage sintering temperature is at 400~550 DEG C, and sintering temperature time control is in 4~12h, and second
Stage sintering temperature is controlled at 650~900 DEG C, and sintering temperature time control is post-processed after being sintered in 10~25h, S03
To dissociate and sieving.
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