CN104409723A - Electrochemical preparation method of ternary anode material - Google Patents
Electrochemical preparation method of ternary anode material Download PDFInfo
- Publication number
- CN104409723A CN104409723A CN201410826843.7A CN201410826843A CN104409723A CN 104409723 A CN104409723 A CN 104409723A CN 201410826843 A CN201410826843 A CN 201410826843A CN 104409723 A CN104409723 A CN 104409723A
- Authority
- CN
- China
- Prior art keywords
- nickel
- preparation
- cobalt
- manganese
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 22
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 22
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 238000001694 spray drying Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 36
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 239000010406 cathode material Substances 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 7
- 229910013716 LiNi Inorganic materials 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- -1 manganese metals Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 abstract 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 238000007259 addition reaction Methods 0.000 abstract 1
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009388 chemical precipitation Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004886 process control Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910012653 LiNi0.5Co0.2Mn0.3 Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- ZYKTVIDNXTWTNS-UHFFFAOYSA-L [Co].[Mn].[Ni](O)O Chemical compound [Co].[Mn].[Ni](O)O ZYKTVIDNXTWTNS-UHFFFAOYSA-L 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 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
- 238000000926 separation method Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 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 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- H01M4/52—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses an electrochemical preparation method of a ternary anode material. According to the method disclosed by the invention, pure nickel, cobalt and manganese metals and electric energy are used as raw materials and a green electrochemical synthesis method is adopted for synthesizing a nickel, cobalt and manganese salt compound by means of electrolysis at normal pressure and normal temperature, and the ternary anode material-LiNixCoyMnzO2 can be obtained after lithium addition reaction, spray-drying and high-temperature treatment, wherein x is greater than 1 and less than 1, y is greater than 0 and less than 0.8, z is greater than 0 and less than 1, and x+y+z is equal to 1. Compared with the prior art, the electrochemical preparation method disclosed by the invention can be used for reducing the cost of raw materials and energy consumption, simplifying the process, also reducing the environmental pollution and improving the product performances. An electrochemical synthesis technology adopted by the method is an environmentally-friendly chemical process, the pure metals are used as anode materials and no impurities are introduced, so that the concentration controllability and the high purity of nickel ions, cobalt ions and manganese ions are guaranteed; meanwhile, the zero emission of wastewater to the environment is realized, and the continuous large-scale production can be realized.
Description
Technical field
The present invention relates to the preparation method of ternary cathode material of lithium ion battery, be specifically related to a kind of electrochemical preparation method of tertiary cathode material.
Background technology
The positive electrode that current lithium ion battery adopts mainly contains cobalt acid lithium, LiFePO4, LiMn2O4 and tertiary cathode material etc.Nickle cobalt lithium manganate tertiary cathode material has that specific capacity is high, security performance and multiplying power discharging property good, be a kind of lithium ion power battery cathode material of great potential, have broad application prospects at dynamic field such as electronic car and boat, electronic spacecraft, electric tools.
The preparation method of current tertiary cathode material mainly contains high temperature solid-phase sintering method and liquid chemical precipitation method.High temperature solid-state method method is simple, but shatters ball milling and be difficult to control, and there is the uneven defect of each starting compound mixing, and sintering temperature is high, and energy consumption is large, is difficult to extensive implementation.Chemical precipitation method can be divided into the indirect chemical precipitation method and direct chemical precipitation method.Compared with conventional solid synthetic method, chemical precipitation method can make material reach mixing in molecule or atomic level, and be easy to obtain the presoma that particle diameter is little, mix, and sintering temperature is lower, synthetic product component is even.But chemical precipitation method LITHIUM BATTERY used nickel source, cobalt source, manganese source material price are high, purity is wayward, and the ternary mixing co-precipitation obtained, needs multiple times of filtration to wash, produce a large amount of waste water, to environment.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of electrochemical preparation method of tertiary cathode material, the method directly uses nickel, cobalt, manganese simple metal and electric energy as raw material, cost is low, technique is simple, and reduces environmental pollution, enhances product performance.
The electrochemical preparation method of a kind of tertiary cathode material provided by the invention, mainly comprises the following steps:
(1), respectively using pure metallic nickel, cobalt, manganese as anode material, negative electrode is made with inert electrode, with acetic acid, citric acid mixed solution for electrolyte, in undivided cell, logical direct current electrolysis, obtains nickel ion solution, cobalt ions solution and manganese ion solution respectively;
(2) after, nickel ion solution, cobalt ions solution and manganese ion solution prepared by step (1) being mixed by a certain percentage, lithium ion is added by the certain mol proportion with nickel ion, cobalt ions and manganese ion total amount, heating stirring reaction, obtains flowing covert suspension-turbid liquid;
(3) the stream covert suspension-turbid liquid high-speed centrifugal spray dryer, by step (2) obtained carries out spraying dry, obtains ternary material precursor, then through high-temperature process in inert atmosphere high temperature furnace, obtains nickel-cobalt-manganternary ternary anode material.
In step (1), the current strength of electrolysis is 0.1-10A/dm
2, described electrolyte is 0.1-4.0mol/L acetic acid, citric acid mixed solution, and wherein the mol ratio of citric acid and acetic acid is 1:1 ~ 5; The nickel ion solution obtained, cobalt ions solution and manganese ion solution concentration are 0.1-3.0mol/L.
In step (2), the mol ratio of nickel ion solution, cobalt ions solution and manganese ion solution mixing is nickel ion: cobalt ions: manganese ion=x:y:z, wherein 0<x<1,0<y<0.8,0<z<1, and x+y+z=1; Nickel ion, cobalt ions and manganese ion total amount are 1:1 ~ 1.4 with the mol ratio of the lithium ion added; Described lithium ion is selected from one or more in lithium hydroxide, lithia, lithium acetate; Described stirring reaction, condition is: stirring reaction 6-28h under temperature is 30-80 DEG C, pH 7-9 condition.
In step (3), spray drying condition control is: feeding flow velocity is 0.2 ~ 10L/min, and inlet temperature is 160 DEG C ~ 320 DEG C, and export environment temperature is 90 DEG C ~ 150 DEG C; Described high-temperature process is the high-temperature process 2-11h of 400-900 DEG C; Prepared tertiary cathode material molecular formula is LiNi
xco
ymn
zo
2, wherein, 0<x<1,0<y<0.8,0<z<1, and x+y+z=1.
Compared with prior art, the invention provides one directly uses pure metallic nickel, cobalt, manganese as nickel source, cobalt source, manganese source material, electrosynthesis glyoxal nickel, cobalt, manganese salt compound under normal pressure and temperature, through adding lithium reaction, spraying dry, high-temperature process obtains the electrochemistry technology of preparing of tertiary cathode material, reduce the cost of raw material and energy consumption, simplify technique, reduce environmental pollution simultaneously, improve properties of product.The electrochemistry formated technology of this method is a kind of environment amenable Green Chemistry process; use simple metal to make anode material, do not introduce any impurity, ensure that the controlled of nickel, cobalt, manganese ion concentration and high-purity; realize the zero discharge of waste water to environment simultaneously, continous way large-scale production can be realized.This method realizes the reaction of molecule, ionic level, can add surface modifier arbitrarily; Product component is even, and consistency is good, and the electric discharge gram volume of the tertiary cathode material product of this method synthesis is high, and multiplying power discharging property is good, and cyclical stability is high.
Accompanying drawing explanation
Fig. 1 is the process chart of electrochemistry formated tertiary cathode material provided by the invention;
Fig. 2 is the charge-discharge performance figure of nickel-cobalt-manganternary ternary anode material prepared by the present invention
Embodiment
In order to understand content of the present invention better, be described further below in conjunction with specific embodiment.Should be understood that these embodiments only for the present invention is further described, and be not used in and limit the scope of the invention.
Embodiment 1
A preparation method for tertiary cathode material, comprises the following steps:
(1) 100L 1.0mol/L acetic acid, citric acid electrolyte, is prepared, wherein containing acetic acid 0.8mol/L, citric acid 0.2mol/L, anode is done respectively with pure metallic nickel, cobalt, manganese, with inert electrode titanium for negative electrode, control electric current 3A electrolysis, electrolysis electricity stops electrolysis to 160F (faraday, 1F=26.8Ah), obtains concentration and is 0.8mol/L nickel, cobalt, manganese ion solution.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ions: the mixed in molar ratio of manganese ion=0.5:0.2:0.3, the lithium hydroxide of slow dropping 1.0mol/L is in the reactor stirred continuously, lithium ion in molar ratio: the mol ratio metering of (nickel ion+cobalt ions+manganese ion)=1.1:1, whole process control temp is at about 50 DEG C stirring reaction 18h, control pH 7.5, obtains flowing covert suspension-turbid liquid.
(3) the stream covert suspension-turbid liquid high-speed centrifugal spray dryer, step (2) obtained carries out spraying dry, feeding flow velocity is 1L/min, inlet temperature is 240 DEG C, leaving air temp is 110 DEG C, flow the spray-dried powdery ternary material precursor obtaining high degree of dispersion fast of covert suspension-turbid liquid, by ternary material precursor in nitrogen atmosphere high temperature furnace, heat up 400 DEG C of insulations 3 hours with the programming rate of 5 DEG C/min, then heat up with the programming rate of 5 DEG C/min and obtain nickel-cobalt-manganternary ternary anode material at 800 DEG C of high-temperature process 8h, its molecular formula is LiNi
0.5co
0.2mn
0.3o
2.
Embodiment 2
A preparation method for tertiary cathode material, comprises the following steps:
(1) 100L 2.0mol/L acetic acid, citric acid electrolyte, is prepared, wherein containing acetic acid 1.2mol/L, citric acid 0.8mol/L, anode is done respectively with pure metallic nickel, cobalt, manganese, with inert electrode stainless steel for negative electrode, control electric current 6A electrolysis, electrolysis electricity stops electrolysis to 240F, obtains concentration and is 1.2mol/L nickel, cobalt, manganese ion solution.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ions: the mixed in molar ratio of manganese ion=1/3:1/3:1/3, the lithium hydroxide of slow dropping 1.0mol/L is in the reactor stirred continuously, lithium ion in molar ratio: the mol ratio metering of (nickel ion+cobalt ions+manganese ion)=1.2:1, whole process control temp is at about 60 DEG C stirring reaction 18h, control pH 8.5, obtains flowing covert suspension-turbid liquid.
(3) the stream covert suspension-turbid liquid high-speed centrifugal spray dryer, step (2) obtained carries out spraying dry, feeding flow velocity is 1L/min, inlet temperature is 238 DEG C, leaving air temp is 106 DEG C, flow the spray-dried powdery ternary material precursor obtaining high degree of dispersion fast of covert suspension-turbid liquid, in nitrogen atmosphere high temperature furnace, heat up 300 DEG C of insulations 4 hours with the programming rate of 5 DEG C/min, then heat up with the programming rate of 5 DEG C/min and obtain nickel-cobalt-manganternary ternary anode material at 850 DEG C of high-temperature process 7h, its molecular formula is LiNi
1/3co
1/3mn
1/3o
2.
Embodiment 3
A preparation method for tertiary cathode material, comprises the following steps:
(1) 100L 2.6mol/L acetic acid, citric acid electrolyte, is prepared, wherein containing acetic acid 1.6mol/L, citric acid 1.0mol/L, anode is done respectively with pure metallic nickel, cobalt, manganese, with inert electrode stainless steel for negative electrode, control electric current 6A electrolysis, electrolysis electricity, to 320F, stops electrolysis, obtains concentration and be 1.6mol/L nickel, cobalt, manganese ion solution.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ions: the mixed in molar ratio of manganese ion=1/3:1/3:1/3, the lithium hydroxide of slow dropping 1.0mol/L is in the reactor stirred continuously, by lithium ion: the mol ratio metering of (nickel ion+cobalt ions+manganese ion)=1.15:1, whole process control temp is at about 50 DEG C stirring reaction 18h, control pH8, obtains flowing covert suspension-turbid liquid.
(3) the stream covert suspension-turbid liquid high-speed centrifugal spray dryer, step (2) obtained carries out spraying dry, feeding flow velocity is 1L/min, inlet temperature is 230 DEG C, leaving air temp is 102 DEG C, flow the spray-dried powdery ternary material precursor obtaining high degree of dispersion fast of covert suspension-turbid liquid, by ternary material precursor in nitrogen atmosphere high temperature furnace, heat up 400 DEG C of insulations 3 hours with the programming rate of 5 DEG C/min, then heat up with the programming rate of 5 DEG C/min and obtain nickel-cobalt-manganternary ternary anode material at 850 DEG C of high-temperature process 8h, its molecular formula is LiNi
1/3co
1/3mn
1/3o
2.
Embodiment 4
A preparation method for tertiary cathode material, comprises the following steps:
(1) 100L 3.0mol/L acetic acid, citric acid electrolyte, is prepared, wherein containing acetic acid 1.8mol/L, citric acid 1.2mol/L, anode is done respectively with pure metallic nickel, cobalt, manganese, with inert electrode stainless steel for negative electrode, control electric current 6A electrolysis, electrolysis electricity stops electrolysis to 360F, obtains concentration and is 1.8mol/L nickel, cobalt, manganese ion solution.
(2), nickel, cobalt, manganese ion solution are pressed nickel ion: cobalt ions: the mixed in molar ratio of manganese ion=0.8:0.2:1, the lithium hydroxide of slow dropping 1.0mol/L is in the reactor stirred continuously, by lithium ion: the mol ratio metering of (nickel ion+cobalt ions+manganese ion)=1.1:1, whole process control temp is at about 50 DEG C stirring reaction 18h, control pH 7.5, obtains flowing covert suspension-turbid liquid.
(3) the stream covert suspension-turbid liquid high-speed centrifugal spray dryer, step (2) obtained carries out spraying dry, feeding flow velocity is 1L/min, inlet temperature is 235 DEG C, leaving air temp is 102 DEG C, flow the spray-dried powdery ternary material precursor obtaining high degree of dispersion fast of covert suspension-turbid liquid, by ternary material precursor in nitrogen atmosphere high temperature furnace, heat up 400 DEG C of insulations 3 hours with the programming rate of 5 DEG C/min, then heating up with the programming rate of 5 DEG C/min obtains nickel-cobalt-manganternary ternary anode material at 850 DEG C of high-temperature process 8h.Its molecular formula is LiNi
0.4co
0.1mn
0.5o
2.
Comparative example 1
(1) nickel taken by the molar ratio of 5:2:3, cobalt, manganese nitrate are dissolved in solution, utilize the sodium hydroxide solution adjust ph of 1mol/L between 8-11, sustained response 20 hours; Separation of Solid and Liquid is carried out, cleaning, dry final acquisition nickel hydroxide cobalt manganese presoma LiNi after reaction terminates
0.5co
0.2mn
0.3(OH)
2.
(2) by the mol ratio of 1.1:1 by CH
3cOOLi2H
20 and LiNi
0.5co
0.2mn
0.3(OH)
2mix by the mode of ball milling, this mixture is removed acetate in 4 hours with the programming rate of 5 DEG C/min 500 DEG C of insulations, then be warming up to 920 DEG C with the programming rate of 5 DEG C/min and carry out double sintering, and finally obtain tertiary cathode material LiNi with stove cooling after being incubated 8 hours at this temperature
0.5co
0.2mn
0.3o
2
Comparative example 2
(1) nickel taken by the molar ratio of 1:1:1, cobalt, manganese nitrate are dissolved in solution, utilize the sodium hydroxide solution adjust ph of 1mol/L between 8-11, sustained response 20 hours; Separation of Solid and Liquid is carried out, cleaning, dry final acquisition nickel hydroxide cobalt manganese presoma Ni after reaction terminates
1/3co
1/3mn
1/3(OH)
2.
(2) by the mol ratio of 1.2:1 by CH
3cOOLi2H
20 and LiNi
0.5co
0.2mn
0.3(OH)
2mix by the mode of ball milling, this mixture is removed acetates with the programming rate of 5 DEG C/min at 500 DEG C of insulation 4 lab scales, then be warming up to 920 DEG C with the programming rate of 5 DEG C/min and carry out double sintering, and finally obtain nickel-cobalt-manganternary ternary anode material LiNi with stove cooling after being incubated 8 hours at this temperature
1/3co
1/3mn
1/3o
2.
Respectively by example 1-4 of the present invention, the tertiary cathode material that comparative example 1 and 2 obtains, polyvinylidene fluoride, acetylene black mix according to the ratio of mass percent 80:12:8, and stir into muddy, evenly be coated in aluminium foil surface, then vacuum drying at 80 DEG C, after tabletted at 90 DEG C vacuum drying again, thus obtained based lithium-ion battery positive plate.
This based lithium-ion battery positive plate and lithium ion battery negative (metal reason sheet) are assembled into lithium ion battery, with microporous polypropylene membrane (cellgard2000) as lithium ion battery separator, with the ethylene carbonate vinegar (EC) of volume ratio 1:1 and carbonic acid diformazan vinegar (DMC) for solvent, by 1mol/L LiPF
6as the electrolyte of lithium ion battery.The lithium ion battery assembled at room temperature is placed after 24 hours and is carried out charge-discharge test, and the voltage range of discharge and recharge is 2.75V ~ 4.5V, and embedding lithium reversible capacity, the charge-discharge performance of lithium ion battery is measured at room temperature circulation.
195mAh/g is reached by the discharge capacity first of lithium ion battery under 0.2C that the tertiary cathode material of this method synthesis makes, after 100 circulations, discharge capacity still has 172mAh/g, and high rate performance is given prominence to, and reaches 185mAh/g and 166mAh/g at 1C and 10C discharge capacity.The contrast of electric discharge gram volume is listed in table 1, and charge-discharge performance is shown in Fig. 2.
Table 1 discharge gram volume contrast
In addition should be understood that in the scope of described aim before and after not departing from, the enforcement of change is included in technical scope of the present invention.After having read content of the present invention, person skilled in art has made some nonessential change or adjustment to the present invention, still belongs to protection scope of the present invention.
Claims (10)
1. an electrochemical preparation method for tertiary cathode material, is characterized in that, described preparation method comprises the following steps:
(1), respectively using pure metallic nickel, cobalt, manganese as anode material, negative electrode is made with inert electrode, with acetic acid, citric acid mixed solution for electrolyte, in undivided cell, logical direct current electrolysis, obtains nickel ion solution, cobalt ions solution and manganese ion solution respectively;
(2) after nickel ion solution, cobalt ions solution and the manganese ion solution mixing, by step (1) prepared, add lithium ion, heating stirring reaction, obtains flowing covert suspension-turbid liquid;
(3) the stream covert suspension-turbid liquid high-speed centrifugal spray dryer, by step (2) obtained carries out spraying dry, obtains ternary material precursor, then through high-temperature process in inert atmosphere high temperature furnace, obtains nickel-cobalt-manganternary ternary anode material.
2. preparation method according to claim 1, is characterized in that, in step (1), the current strength of electrolysis is 0.1-10A/dm
2, the nickel ion solution obtained, cobalt ions solution and manganese ion solution concentration are 0.1-3.0mol/L.
3. preparation method according to claim 1, is characterized in that, electrolyte described in step (1) is 0.1-4.0mol/L acetic acid, citric acid mixed solution, and wherein the mol ratio of citric acid and acetic acid is 1:1 ~ 5.
4. preparation method according to claim 1, it is characterized in that, in step (2), the mol ratio of nickel ion solution, cobalt ions solution and manganese ion solution mixing is nickel ion: cobalt ions: manganese ion=x:y:z, wherein 0<x<1,0<y<0.8,0<z<1, and x+y+z=1.
5. preparation method according to claim 1, is characterized in that, mol ratio 1:1 ~ 1.4 of nickel ion, cobalt ions and manganese ion total amount and the lithium ion added in step (2).
6. preparation method according to claim 1, is characterized in that, described in step (2), lithium ion is selected from one or more in lithium hydroxide, lithia, lithium acetate.
7. preparation method according to claim 1, is characterized in that, step heats stirring reaction described in (2), and condition is: stirring reaction 6-28h under temperature is 30-80 DEG C, pH 7-9 condition.
8. preparation method according to claim 1, is characterized in that, in step (3), spray drying condition control is: feeding flow velocity is 0.2 ~ 10L/min, and inlet temperature is 160 DEG C ~ 320 DEG C, and export environment temperature is 90 DEG C ~ 150 DEG C.
9. preparation method according to claim 1, is characterized in that, high-temperature process described in step (3) is the high-temperature process 2-11h of 400-900 DEG C.
10. preparation method according to claim 1, is characterized in that, the tertiary cathode material molecular formula prepared is LiNi
xco
ymn
zo
2, wherein, 0<x<1,0<y<0.8,0<z<1, and x+y+z=1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410826843.7A CN104409723B (en) | 2014-12-25 | 2014-12-25 | A kind of electrochemical preparation method of tertiary cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410826843.7A CN104409723B (en) | 2014-12-25 | 2014-12-25 | A kind of electrochemical preparation method of tertiary cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104409723A true CN104409723A (en) | 2015-03-11 |
| CN104409723B CN104409723B (en) | 2016-09-28 |
Family
ID=52647333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410826843.7A Active CN104409723B (en) | 2014-12-25 | 2014-12-25 | A kind of electrochemical preparation method of tertiary cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104409723B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018094819A1 (en) * | 2016-11-25 | 2018-05-31 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery |
| CN109680333A (en) * | 2019-01-04 | 2019-04-26 | 南通瑞翔新材料有限公司 | A kind of wet preparation method of high Ni-monocrystal positive electrode |
| CN111725499A (en) * | 2020-06-29 | 2020-09-29 | 天津理工大学 | Method for preparing lithium battery cathode material NCM811 by using co-precipitation method with electrolytic method |
| US20210359300A1 (en) * | 2020-05-14 | 2021-11-18 | Nano One Materials Corp. | Alternative Method for Making Lithium Battery Cathode Materials |
| US11749842B2 (en) | 2018-11-05 | 2023-09-05 | Tesla, Inc. | Cell with a tabless electrode |
| US11909041B2 (en) | 2018-04-04 | 2024-02-20 | Tesla, Inc. | Method to produce cathode materials for Li-ion batteries |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101237041A (en) * | 2008-01-29 | 2008-08-06 | 四川大学 | Method for making lithium-included pole material with inter-metal compound of multi-element metal |
| US20090297950A1 (en) * | 2008-05-30 | 2009-12-03 | Dongguan Amperex Technology Co., Ltd. | Lithium battery |
| CN103259008A (en) * | 2013-04-12 | 2013-08-21 | 湖北文理学院 | Ternary composite positive electrode material of lithium ion battery and preparation method thereof |
-
2014
- 2014-12-25 CN CN201410826843.7A patent/CN104409723B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101237041A (en) * | 2008-01-29 | 2008-08-06 | 四川大学 | Method for making lithium-included pole material with inter-metal compound of multi-element metal |
| US20090297950A1 (en) * | 2008-05-30 | 2009-12-03 | Dongguan Amperex Technology Co., Ltd. | Lithium battery |
| CN103259008A (en) * | 2013-04-12 | 2013-08-21 | 湖北文理学院 | Ternary composite positive electrode material of lithium ion battery and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018094819A1 (en) * | 2016-11-25 | 2018-05-31 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery |
| US11909041B2 (en) | 2018-04-04 | 2024-02-20 | Tesla, Inc. | Method to produce cathode materials for Li-ion batteries |
| US11749842B2 (en) | 2018-11-05 | 2023-09-05 | Tesla, Inc. | Cell with a tabless electrode |
| CN109680333A (en) * | 2019-01-04 | 2019-04-26 | 南通瑞翔新材料有限公司 | A kind of wet preparation method of high Ni-monocrystal positive electrode |
| US20210359300A1 (en) * | 2020-05-14 | 2021-11-18 | Nano One Materials Corp. | Alternative Method for Making Lithium Battery Cathode Materials |
| CN111725499A (en) * | 2020-06-29 | 2020-09-29 | 天津理工大学 | Method for preparing lithium battery cathode material NCM811 by using co-precipitation method with electrolytic method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104409723B (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102569776B (en) | Preparation method of spinel type lithium manganese oxide for spherical high-voltage anode material | |
| CN103872315B (en) | A kind of preparation method of cobalt acid lithium composite positive pole of Ge-doped high-energy-density | |
| CN103311532B (en) | Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure | |
| CN104409723B (en) | A kind of electrochemical preparation method of tertiary cathode material | |
| CN103825015B (en) | The preparation method of high compacted density nickle cobalt lithium manganate NCM523 ternary material | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN101335348A (en) | Preparing method of lithium ionic cell 5V anode material spherical LiNi*Mn*O* | |
| CN108493458B (en) | High-performance echinoid nickel oxide/nickel cobaltate microsphere lithium oxygen battery positive electrode catalytic material and preparation method thereof | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN110589791B (en) | Preparation method of tin-doped titanium pyrophosphate | |
| CN103928676A (en) | Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof | |
| CN110233261B (en) | Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery | |
| CN105609758A (en) | Preparation method of rubdium- and cesium-doped lithium-rich ternary cathode material for lithium-ion battery | |
| CN113036118B (en) | Positive electrode material and preparation method and application thereof | |
| CN112758991A (en) | Preparation method of core-shell structure ternary cathode material precursor | |
| CN107394178B (en) | Cobalt carbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
| CN110615480A (en) | Method for preparing layered lithium manganate material by dynamic hydrothermal method | |
| CN108365216A (en) | The novel nickelic tertiary cathode material of one kind and preparation | |
| CN109950523A (en) | Lithium ion battery negative material transition metal oxide/carbon preparation method | |
| CN102903918B (en) | Preparation method for manganese phosphate lithium nanosheet | |
| CN101704681A (en) | Method for preparing lithium titanate with spinel structure | |
| CN111342008A (en) | Potassium fluoride doped lithium-rich manganese-based material and preparation method and application thereof | |
| CN117185354A (en) | Sodium manganate positive electrode material with high sodium content and preparation method and application thereof | |
| CN1562771A (en) | Spherical shaped lithium manganate and preparation method | |
| CN106159220B (en) | two-step method for preparing lithium ion battery anode material L iNi0.80Co0.15Al0.05O2Method (2) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170525 Address after: 332000 Jiangxi Province, Jiujiang Ruichang City Economic Development Zone South East Ring Road Patentee after: Jiujiang Hua Yang battery material Co.,Ltd. Address before: 241009 Anhui city of Wuhu Province Economic and Technological Development Zone Branch Center, No. 222 D220 Patentee before: WUHU HUAXINNUO ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20171207 Address after: 241000 Anhui city of Wuhu Province Economic and Technological Development Zone Branch Center, No. 222 D220 Patentee after: WUHU HUAXINNUO ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. Address before: 332000 Jiangxi Province, Jiujiang Ruichang City Economic Development Zone South East Ring Road Patentee before: Jiujiang Hua Yang battery material Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200713 Address after: Room 308, building 8, University Science Park, 5699 North Second Ring Road, Baoding City, Hebei Province 071000 Patentee after: ANBAIRUI HEBEI ENERGY TECHNOLOGY Co.,Ltd. Address before: 241000 Anhui city of Wuhu Province Economic and Technological Development Zone Branch Center, No. 222 D220 Patentee before: WUHU HUAXINNUO ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210826 Address after: 241000 No. 220 and 222, D Park, science and innovation center, Wuhu Economic and Technological Development Zone, Anhui Province Patentee after: WUHU HUAXINNUO ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. Address before: 071000 Room 308, building 8, University Science Park, 5699 North 2nd Ring Road, Baoding City, Hebei Province Patentee before: ANBAIRUI HEBEI ENERGY TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220128 Address after: 230000 No. 407, B2, Huayi Science Park, No. 71, Tianda Road, high tech Zone, Hefei, Anhui Province Patentee after: Hefei Zeshan New Energy Technology Co.,Ltd. Address before: 241000 No. 220 and 222, D Park, science and innovation center, Wuhu Economic and Technological Development Zone, Anhui Province Patentee before: WUHU HUAXINNUO ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221118 Address after: 241009 Floor 6, Building A, R&D Pilot Building, No. 1, Henglangshan Road, Wuhu Hi tech Industrial Development Zone, Yijiang District, Wuhu City, Anhui Province Patentee after: WUHU HUAXINNUO ELECTROCHEMICAL TECHNOLOGY Co.,Ltd. Address before: 230000 No. 407, B2, Huayi Science Park, No. 71, Tianda Road, high tech Zone, Hefei, Anhui Province Patentee before: Hefei Zeshan New Energy Technology Co.,Ltd. |