CN114613987B - Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof - Google Patents
Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN114613987B CN114613987B CN202210283165.9A CN202210283165A CN114613987B CN 114613987 B CN114613987 B CN 114613987B CN 202210283165 A CN202210283165 A CN 202210283165A CN 114613987 B CN114613987 B CN 114613987B
- Authority
- CN
- China
- Prior art keywords
- gradient
- nickel
- lithium manganate
- nickel cobalt
- cobalt lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000001354 calcination Methods 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 239000010405 anode material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 28
- 230000002829 reductive effect Effects 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 42
- 239000012266 salt solution Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 4
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006184 cosolvent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 238000000840 electrochemical analysis Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 239000011258 core-shell material Substances 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 5
- 239000011257 shell material Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 9
- 150000004682 monohydrates Chemical class 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 229910052810 boron oxide Inorganic materials 0.000 description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- -1 ammonia ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 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
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical group CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a nickel cobalt lithium manganate gradient positive electrode material and a preparation method thereof. The preparation method comprises the following steps: obtaining a nickel cobalt lithium manganate gradient anode material precursor; the nickel content in the nickel cobalt lithium manganate gradient anode material precursor is reduced from the inner core to the outer shell in a gradient manner, and the cobalt and manganese content is increased from the inner core to the outer shell in a gradient manner; uniformly mixing a precursor of the nickel cobalt lithium manganate gradient anode material with a lithium source, and then carrying out gradient calcination to obtain the nickel cobalt lithium manganate gradient anode material; wherein, the gradient calcining process comprises the following steps: the calcination temperature is controlled so that the calcination temperature gradient is reduced. According to the invention, the core-shell is subjected to respective optimal sintering conditions through temperature gradient calcination, so that the core-shell component and the structure difference in the sintering process are prevented from shrinking and gradually separating in different degrees in the circulating process, and the long-term circulating performance of the material is effectively improved.
Description
Technical Field
The invention relates to the technical field of positive electrode materials, in particular to a nickel cobalt lithium manganate gradient positive electrode material and a preparation method thereof.
Background
The nickel cobalt lithium manganate ternary lithium ion battery anode material is widely applied to the field of new energy automobiles due to high energy density.
High nickel enrichment is generally employed to maximize reversible capacity. However, as the nickel content increases, the cation mix of the high nickel material becomes more and more, and the cycle and thermal stability gradually decrease, thereby resulting in a decrease in the cycle life of the battery. Thus, there is a study to improve the stability of the material interface and the cycle life of the battery by controlling the nickel content from the core to the particle surface to gradually decrease, i.e., higher nickel content in the core contributes to higher discharge capacity, and higher cobalt manganese content in the outer layer provides more structural stability. However, the difference in composition and structure between the core and the shell occurs during sintering, so that the core and the shell shrink to different degrees during circulation and gradually separate, thereby inhibiting the diffusion-migration process of ions/electrons between the core and the shell, and causing the material to be degraded in long-term circulation performance.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a nickel cobalt lithium manganate gradient positive electrode material and a preparation method thereof, and solves the technical problem that the material performance is reduced due to unreasonable sintering process of the nickel cobalt lithium manganate gradient positive electrode material with gradient change of nickel content in the prior art.
During the test, the inventors found that, since the nickel content gradually increases from the outer shell to the inner core, the nickel in the inner core portion gradually diffuses toward the surface during the sintering due to the concentration diffusion mechanism, the manganese and cobalt contents of the surface are higher than the inner core, gradually diffuses toward the inside, and theoretically the optimum calcination temperature from the core to the shell is gradually increased. It is therefore desirable to subject the core-shell to respective optimum sintering conditions by temperature gradient calcination to avoid the occurrence of core-shell composition and structural differences during sintering, resulting in different degrees of shrinkage and gradual separation of the core-shell during cycling, thereby improving the long-term cycling performance of the material.
Based on the above, the first aspect of the invention provides a preparation method of a nickel cobalt lithium manganate gradient positive electrode material, which comprises the following steps:
obtaining a nickel cobalt lithium manganate gradient anode material precursor; the nickel content in the nickel cobalt lithium manganate gradient anode material precursor is reduced from the inner core to the outer shell in a gradient manner, and the cobalt and manganese content is increased from the inner core to the outer shell in a gradient manner;
uniformly mixing the precursor of the nickel cobalt lithium manganate gradient anode material with a lithium source, and then carrying out gradient calcination to obtain the nickel cobalt lithium manganate gradient anode material; wherein, the gradient calcining process comprises the following steps: the calcination temperature is controlled so that the calcination temperature gradient is reduced.
The second aspect of the invention provides a nickel cobalt lithium manganate gradient positive electrode material, which is obtained by the preparation method of the nickel cobalt lithium manganate gradient positive electrode material provided by the first aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the core-shell is subjected to respective optimal sintering conditions through temperature gradient calcination, so that the core-shell component and the structure difference in the sintering process are prevented from shrinking and gradually separating in different degrees in the circulating process, and the long-term circulating performance of the material is effectively improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The first aspect of the invention provides a preparation method of a nickel cobalt lithium manganate gradient positive electrode material, which comprises the following steps:
s1, obtaining a nickel cobalt lithium manganate gradient anode material precursor; the nickel content in the nickel cobalt lithium manganate gradient anode material precursor is reduced from the inner core to the outer shell in a gradient manner, and the cobalt and manganese content is increased from the inner core to the outer shell in a gradient manner;
s2, uniformly mixing the precursor of the nickel cobalt lithium manganate gradient anode material with a lithium source, and then carrying out gradient calcination to obtain the nickel cobalt lithium manganate gradient anode material; wherein, the gradient calcining process comprises the following steps: the calcination temperature is controlled so that the calcination temperature gradient is reduced.
In the invention, the step of obtaining the nickel cobalt lithium manganate gradient anode material precursor comprises the following steps:
s11, preparing n groups of mixed salt solutions containing nickel sources, cobalt sources and manganese sources with different nickel contents; wherein n is a positive integer not less than 2; in some embodiments of the invention, n is 3; the nickel source is at least one of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate, the cobalt source is at least one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate, and the manganese source is at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate. In some embodiments of the invention, the nickel cobalt manganese metal molar ratio is 5:2: 3. 7:1:2 and 90:5:5, respectively preparing a nickel source, a cobalt source and a manganese source into mixed salt solutions with three metal proportions, namely an A metal salt solution, a B metal salt solution and a C metal salt solution; further, in the mixed salt solution, the concentration of total metal ions of nickel, cobalt and manganese is 1-3 mol/L.
S12, preparing an alkali solution and a complexing agent solution; wherein the alkali is at least one of sodium hydroxide and potassium hydroxide; the concentration of the alkali solution is 2-6 mol/L, and further 4mol/L; the complexing agent is at least one of ammonia water and citric acid; the concentration of the complexing agent solution is 0.5-5 mol/L, and further 1mol/L.
S13, mixing n groups of mixed salt solutions with different nickel contents with an alkali solution and a complexing agent solution in sequence, and carrying out continuous reaction to prepare a nickel cobalt lithium manganate gradient anode material precursor; wherein the reaction temperature is controlled between 40 ℃ and 60 ℃, the reaction pH is between 10 and 13, and nitrogen is used as protection in the reaction process.
In the step S13 of the invention, the steps of mixing n groups of mixed salt solutions with different nickel contents with an alkali solution and a complexing agent solution in sequence for continuous reaction comprise the following steps:
s131, introducing the 1 st group of mixed salt solution, the alkali solution and the complexing agent solution into a reaction container for reaction to obtain a 1 st reaction solution;
s132, mixing and reacting the ith reaction solution, the (i+1) th mixed salt solution, the alkali solution and the complexing agent solution to obtain the (i+1) th reaction solution;
s133, repeating the step S132 to sequentially perform a mixing reaction until an nth reaction solution is obtained, and aging, filtering, washing and drying the nth reaction solution to obtain a nickel cobalt lithium manganate gradient anode material precursor;
wherein i is a positive integer, i is more than or equal to 1 and less than i+1 and less than n, the nickel content of the i-th group mixed salt solution is greater than the nickel content of the i+1-th group mixed salt solution, and the cobalt manganese content of the i-th group mixed salt solution is less than the cobalt manganese content of the i+1-th group mixed salt solution, so that the gradient decrease of the nickel content from the inner core to the outer shell and the gradient increase of the cobalt and manganese content from the inner core to the outer shell are realized.
In some preferred embodiments of the invention, the mixed salt solution, the alkali solution and the complexing agent are all introduced into the reaction system at a certain flow rate.
In some embodiments of the invention, the nickel cobalt manganese metal molar ratio is 5:2: 3. 7:1:2 and 90:5: and 5, respectively preparing a nickel source, a cobalt source and a manganese source into mixed salt solutions with the total metal ion concentration of 1-3 mol/L, namely an A metal salt solution, a B metal salt solution and a C metal salt solution, wherein the introducing rates of the mixed salt solution, an alkali solution and a complexing agent solution are respectively 1mol/h, 0.5mol/h and 2mol/h, and the reaction time of the A metal salt solution, the B metal salt solution and the C metal salt solution is respectively 4h, 6h and 20h.
In the present invention, the lithium source is lithium hydroxide or lithium carbonate. In some embodiments of the invention, the lithium source is lithium hydroxide monohydrate (LiOH. H 2 O). Further, the molar ratio of the precursor of the lithium nickel cobalt manganese oxide gradient positive electrode material to the lithium source is 1: (1.01-1.1), in some embodiments of the invention, the molar ratio of the nickel cobalt lithium manganate gradient positive electrode material precursor to the lithium source is 1:1.04.
According to the invention, the calcination temperature is controlled according to the optimal sintering temperature of each layer of the nickel cobalt lithium manganate gradient positive electrode material precursor so as to lead the calcination temperature gradient to be reduced, and each layer of structure is respectively positioned at the respective optimal sintering temperature so as to avoid the shrinkage of different degrees and gradual separation of the core shell in the cyclic process caused by the core shell component and structure difference in the sintering process, thereby improving the long-term cyclic performance of the material. The optimal sintering temperature of each layer of the precursor of the nickel cobalt lithium manganate gradient positive electrode material is obtained by carrying out primary sintering DOE test on lithium salt and precursors of the nickel cobalt lithium manganate ternary positive electrode material with different compositions at different temperatures, the fluctuation range of different proportions is +/-0.01 due to the reasons of time and cost, the fluctuation range of different temperatures is generally +/-10 ℃, and the sintering parameters (temperatureEtc.) are optimal values, which is known in the art and will not be described in detail herein. In some embodiments of the invention, precursor hydroxide Ni is subjected to DOE experiments 0.81 Co 0.08 Mn 0.11 (OH) 2 The optimum sintering temperature of (a) is 800-820 ℃, and the precursor hydroxide Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 The optimal sintering temperature of (a) is 900-920 ℃, and the precursor hydroxide Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 The optimum sintering temperature of (a) is 840-860 ℃, and the precursor hydroxide Ni 0.90 Co 0.05 Mn 0.05 (OH) 2 The optimum sintering temperature of (C) is 740-760 ℃. Further, the process of gradient calcination is performed under an oxygen atmosphere.
In some preferred embodiments of the present invention, the sintering time corresponding to the lowest sintering temperature is 6 to 12 hours, and the sintering time corresponding to the other sintering temperatures except the lowest sintering temperature is 0.5 to 1.5 hours. In the time range, the obtained nickel cobalt lithium manganate gradient positive electrode material has better battery performance.
In some preferred embodiments of the present invention, a fluxing agent is also added during the gradient calcination process described above. According to the invention, the fluxing agent is introduced in the gradient calcination process, so that the calcination temperature of the shell part can be reduced, the shell material is recrystallized at a relatively low temperature, the temperature difference between the shell part and the core part of the outer layer is reduced, the composition and structural difference between the core and the shell in the sintering process are weakened, the core and the shell shrink and separate to different degrees in the circulation process, and finally the circulation performance of the anode material is improved. However, the addition amount of the flux should not be too high. Preferably, the molar ratio of the precursor of the lithium nickel cobalt manganese oxide gradient positive electrode material to the cosolvent is 1: (0.00001 to 0.003), and more preferably 1: (0.00001-0.001); the cosolvent is selected from at least one of oxides, hydroxides, carbonates or chlorides of boron, silicon, magnesium and calcium.
The second aspect of the invention provides a nickel cobalt lithium manganate gradient positive electrode material, which is obtained by the preparation method of the nickel cobalt lithium manganate gradient positive electrode material provided by the first aspect of the invention.
In the following examples and comparative examples of the present invention, the preparation process of the gradient precursor hydroxide with gradually decreasing nickel content from core to shell is as follows:
according to the molar ratio of nickel, cobalt and manganese of 5:2: 3. 7:1:2 and 90:5:5, respectively NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 O is prepared into a mixed salt solution of A, B, C with the total metal ion concentration of 2mol/L and three metal proportions; preparing 1mol/L ammonia water solution and 4mol/L sodium hydroxide solution; firstly, simultaneously pumping a high nickel metal salt solution, a NaOH solution and an ammonia water solution in the C into a reaction kettle according to pump speeds of 1mol/h, 0.5mol/h and 2mol/h, controlling the reaction temperature to be between 40 and 60 ℃, controlling the reaction pH to be between 10 and 13, and taking nitrogen as a protection in the reaction process; in the process, metal ions introduced into the kettle are complexed by ammonia ions to form a large number of cores uniformly; after the reaction is carried out for 20 hours, switching the C into the B metal salt solution, and introducing the B metal salt solution into the kettle to form an intermediate buffer layer; after the reaction is continued for 6 hours, introducing the mixed salt solution A into the kettle, and ending after the reaction is continued for 4 hours; aging, filtering, washing and drying to obtain gradient precursor hydroxide Ni with gradually reduced nickel content from core to shell 0.81 Co 0.08 Mn 0.11 (OH) 2 。
Example 1
Gradient precursor hydroxide, liOH monohydrate and boron oxide are mixed according to the following ratio of 1:1.04: and (3) weighing the materials according to the molar ratio of 0.001, uniformly mixing the materials in a ball milling tank, placing the mixture in an oxygen atmosphere furnace for gradient calcination, and cooling, crushing and sieving the mixture after the reaction is finished to obtain the gradient anode material. Wherein, the gradient calcination process specifically comprises: firstly, the temperature is increased from room temperature to 900 ℃ according to the heating rate of 2 ℃/min, the temperature is kept for 1h, then the temperature is reduced to 850 ℃ according to the cooling rate of 5 ℃/min, the heat is kept for 1h, and finally, the temperature is reduced to 750 ℃ and then kept for 10h.
Example 2
Gradient precursor hydroxide, liOH monohydrate, was prepared according to 1:1.04, placing the mixture in a ball milling tank for uniform mixing, placing the mixture in an oxygen atmosphere furnace for gradient calcination, and cooling, crushing and sieving after the reaction is finished to obtain the gradient anode material. Wherein, the gradient calcination process specifically comprises: firstly, the temperature is increased from room temperature to 920 ℃ according to the heating rate of 2 ℃/min, the temperature is kept for 1h, then the temperature is reduced to 850 ℃ according to the cooling rate of 5 ℃/min, the heat is kept for 1h, and finally, the temperature is reduced to 750 ℃ and then the heat is kept for 10h.
Example 3
Gradient precursor hydroxide, liOH monohydrate and boron oxide were mixed according to 1:1.04: and (3) weighing the materials according to the molar ratio of 0.003, uniformly mixing the materials in a ball milling tank, placing the mixture in an oxygen atmosphere furnace for gradient calcination, and cooling, crushing and sieving the mixture after the reaction is finished to obtain the gradient anode material. Wherein, the gradient calcination process specifically comprises: firstly, the temperature is raised from room temperature to 900 ℃ according to the heating rate of 2 ℃/min, the temperature is kept for 1h, then the temperature is reduced to 850 ℃ according to the cooling rate of 5 ℃/min, the heat is kept for 1h, and finally the temperature is reduced to 750 ℃ and kept for 10h.
Example 4
Gradient precursor hydroxide, liOH monohydrate and boron oxide were mixed according to 1:1.04: and (3) weighing the materials according to the molar ratio of 0.005, uniformly mixing the materials in a ball milling tank, placing the mixture in an oxygen atmosphere furnace for gradient calcination, and cooling, crushing and sieving the mixture after the reaction is finished to obtain the gradient anode material. Wherein, the gradient calcination process specifically comprises: firstly, the temperature is raised from room temperature to 900 ℃ according to the heating rate of 2 ℃/min, the temperature is kept for 1h, then the temperature is reduced to 850 ℃ according to the cooling rate of 5 ℃/min, the heat is kept for 1h, and finally the temperature is reduced to 750 ℃ and kept for 10h.
Comparative example 1
Gradient precursor hydroxide, liOH monohydrate and boron oxide are mixed according to the following ratio of 1:1.04: and (3) weighing the materials according to the molar ratio of 0.001, uniformly mixing the materials in a ball milling tank, placing the mixture in an oxygen atmosphere furnace for gradient calcination, and cooling, crushing and sieving the mixture after the reaction is finished to obtain the gradient anode material. Wherein, the gradient calcination process specifically comprises: firstly, the temperature is raised to 750 ℃ from room temperature according to the heating rate of 2 ℃/min, the temperature is kept for 10 hours, then the temperature is raised to 850 ℃, the heat is kept for 1 hour, and finally the temperature is raised to 900 ℃ and then the heat is kept for 1 hour.
Comparative example 2
Gradient precursor hydroxide, liOH monohydrate and boron oxide are mixed according to the following ratio of 1:1.04: and (3) weighing the materials according to the molar ratio of 0.001, uniformly mixing the materials in a ball milling tank, placing the mixture in an oxygen atmosphere furnace for gradient calcination, and cooling, crushing and sieving the mixture after the reaction is finished to obtain the gradient anode material. Wherein, the gradient calcination process specifically comprises: firstly, the temperature is raised from room temperature to 900 ℃ according to the heating rate of 2 ℃/min, the temperature is kept for 4 hours, then the temperature is reduced to 850 ℃ according to the cooling rate of 5 ℃/min, the heat is kept for 4 hours, and finally, the temperature is reduced to 750 ℃ and then the heat is kept for 4 hours.
Comparative example 3
Gradient precursor hydroxide, liOH monohydrate, was prepared according to 1:1.04, placing the mixture in a ball milling tank for uniform mixing, placing the mixture in an oxygen atmosphere furnace for calcination, and cooling, crushing and sieving after the reaction is finished to obtain the gradient anode material. Wherein the calcination process comprises the following steps: the temperature was raised to 820℃and incubated for 12h.
Comparative example 4
Gradient precursor hydroxide, liOH monohydrate and boron oxide were mixed according to 1:1.04: and (3) weighing the materials according to the molar ratio of 0.001, uniformly mixing the materials in a ball milling tank, placing the mixture in an oxygen atmosphere furnace for calcining, and cooling, crushing and sieving the mixture after the reaction is finished to obtain the gradient anode material. Wherein the calcination process comprises the following steps: the temperature is raised to 800 ℃ and the temperature is kept for 12 hours.
Test group
The prepared anode material is respectively mixed with acetylene black serving as a conductive agent, and PVDF serving as a binder is prepared according to a mass ratio of 92:4: mixing uniformly in proportion, adding a proper amount of 1-methyl-2 pyrrolidone, ball milling for 1 hour to prepare slurry, uniformly coating the slurry on an aluminum sheet, and drying and tabletting to prepare the positive plate. The metal lithium sheet is used as a negative electrode to assemble a 2032 button cell, a blue electric test system is used for electric performance test, the charge-discharge voltage is 2.5-4.25V, the first circle is tested according to 0.2/0.2C charge-discharge, and then the first circle is circulated for 50 circles according to 0.5C/1C. The specific test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the gradient cathode materials obtained in examples 1 to 4 of the present invention clearly have better cycle performance.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (6)
1. The preparation method of the nickel cobalt lithium manganate gradient positive electrode material is characterized by comprising the following steps of:
obtaining a nickel cobalt lithium manganate gradient anode material precursor; the nickel content in the nickel cobalt lithium manganate gradient anode material precursor is reduced from the inner core to the outer shell in a gradient manner, and the cobalt and manganese content is increased from the inner core to the outer shell in a gradient manner; the step of obtaining the nickel cobalt lithium manganate gradient positive electrode material precursor comprises the following steps: s11, preparing n groups of mixed salt solutions containing nickel sources, cobalt sources and manganese sources with different nickel contents; s12, preparing an alkali solution and a complexing agent solution; s13, mixing n groups of mixed salt solutions with different nickel contents with an alkali solution and a complexing agent solution in sequence, and carrying out continuous reaction to prepare a nickel cobalt lithium manganate gradient anode material precursor; the step of mixing n groups of mixed salt solutions with different nickel contents with an alkali solution and a complexing agent solution in sequence for continuous reaction comprises the following steps: s131, introducing the 1 st group of mixed salt solution, the alkali solution and the complexing agent solution into a reaction container for reaction to obtain a 1 st reaction solution; s132, mixing and reacting the ith reaction solution, the (i+1) th mixed salt solution, the alkali solution and the complexing agent solution to obtain the (i+1) th reaction solution; s133, repeating the step S132 to sequentially perform a mixing reaction until an nth reaction solution is obtained, and aging, filtering, washing and drying the nth reaction solution to obtain a nickel cobalt lithium manganate gradient anode material precursor; wherein n is a positive integer more than or equal to 2, i is a positive integer, i is more than or equal to 1 and less than i+1 and less than or equal to n, the nickel content of the i-th mixed salt solution is greater than the nickel content of the i+1-th mixed salt solution, and the cobalt-manganese content of the i-th mixed salt solution is less than the cobalt-manganese content of the i+1-th mixed salt solution;
uniformly mixing the precursor of the nickel cobalt lithium manganate gradient anode material with a lithium source, and then carrying out gradient calcination to obtain the nickel cobalt lithium manganate gradient anode material; wherein, the gradient calcining process comprises the following steps: controlling the calcination temperature according to the optimal sintering temperature of each layer of the nickel cobalt lithium manganate gradient anode material precursor to reduce the calcination temperature gradient; the optimal sintering temperature of each layer of the nickel cobalt lithium manganate gradient positive electrode material precursor is obtained by performing primary sintering DOE tests on lithium salt and nickel cobalt lithium manganate ternary positive electrode material precursors with different compositions at different temperatures, and the sintering temperature with the largest discharge specific capacity and the best cycle performance is the optimal sintering temperature after electrochemical tests of the nickel cobalt lithium manganate ternary positive electrode material obtained by the DOE tests; the sintering time corresponding to the lowest sintering temperature is 6-12 h, and the sintering time corresponding to the other sintering temperatures except the lowest sintering temperature is 0.5-1.5 h.
2. The method for preparing a lithium nickel cobalt manganese oxide gradient positive electrode material according to claim 1, wherein n is 3, and the preparing n groups of mixed salt solutions containing nickel sources, cobalt sources and manganese sources having different nickel contents comprises: according to the molar ratio of nickel, cobalt and manganese of 5:2: 3. 7:1:2 and 90:5: and 5, respectively preparing a nickel source, a cobalt source and a manganese source into mixed salt solutions with three metal ratios.
3. The preparation method of the nickel cobalt lithium manganate gradient anode material according to claim 1, wherein n groups of mixed salt solutions with different nickel contents are sequentially mixed with an alkali solution and a complexing agent solution, the reaction temperature is controlled to be 40-60 ℃ in the step of continuous reaction, the reaction pH is 10-13, and nitrogen is used as a protection in the reaction process.
4. The method for preparing a lithium nickel cobalt manganese oxide gradient positive electrode material according to claim 1, wherein the gradient calcination process is performed under an oxygen atmosphere.
5. The method for preparing the nickel cobalt lithium manganate gradient positive electrode material according to claim 1, wherein a fluxing agent is further added in the gradient calcination process, and the molar ratio of the nickel cobalt lithium manganate gradient positive electrode material precursor to the cosolvent is 1: (0.00001-0.003); the cosolvent is selected from at least one of oxides, hydroxides, carbonates or chlorides of boron, silicon, magnesium and calcium.
6. The nickel cobalt lithium manganate gradient positive electrode material is characterized by being obtained by the preparation method of the nickel cobalt lithium manganate gradient positive electrode material according to any one of claims 1-5.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210283165.9A CN114613987B (en) | 2022-03-22 | 2022-03-22 | Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof |
| PCT/CN2022/108632 WO2023178900A1 (en) | 2022-03-22 | 2022-07-28 | Lithium nickel manganese cobalt oxide gradient positive electrode material and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210283165.9A CN114613987B (en) | 2022-03-22 | 2022-03-22 | Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114613987A CN114613987A (en) | 2022-06-10 |
| CN114613987B true CN114613987B (en) | 2024-03-29 |
Family
ID=81864730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210283165.9A Active CN114613987B (en) | 2022-03-22 | 2022-03-22 | Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114613987B (en) |
| WO (1) | WO2023178900A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114613987B (en) * | 2022-03-22 | 2024-03-29 | 格林美（无锡）能源材料有限公司 | Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof |
| CN115259244B (en) * | 2022-08-31 | 2023-10-17 | 宁波容百新能源科技股份有限公司 | Cobalt gradient high-nickel ternary positive electrode material, preparation method thereof and lithium ion battery |
| CN115403074A (en) * | 2022-09-26 | 2022-11-29 | 湘潭大学 | High-nickel cobalt lithium manganate precursor and preparation method thereof |
| CN115676914A (en) * | 2022-10-27 | 2023-02-03 | 荆门市格林美新材料有限公司 | Production method of positive electrode material precursor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700845A (en) * | 2013-12-18 | 2014-04-02 | 江苏科捷锂电池有限公司 | Preparation method of concentration gradient distributed lithium, nickel, cobalt, manganese and oxygen ternary lithium battery cathode material |
| CN104241640A (en) * | 2014-10-10 | 2014-12-24 | 国家电网公司 | Lithium nickel-cobalt-aluminum positive electrode material, preparation method thereof and lithium ion battery |
| CN105226270A (en) * | 2015-10-22 | 2016-01-06 | 北京科技大学 | There is Li, Ni, Mn oxide positive electrode of nickel manganese concentration gradient and preparation method thereof |
| CN106207138A (en) * | 2016-09-20 | 2016-12-07 | 中国科学院化学研究所 | A kind of method for preparing anode material of lithium-ion battery and application thereof |
| CN111769277A (en) * | 2020-06-30 | 2020-10-13 | 中国科学院上海微系统与信息技术研究所 | Gradient single crystal high-nickel cathode material and preparation method thereof |
| CN112928253A (en) * | 2021-01-22 | 2021-06-08 | 厦门厦钨新能源材料股份有限公司 | Nickel-manganese-titanium composite material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367704B (en) * | 2012-04-06 | 2016-05-11 | 协鑫动力新材料（盐城）有限公司 | Composite multi-component material presoma that gradient distributes and its preparation method and application |
| JP6631320B2 (en) * | 2016-02-29 | 2020-01-15 | 住友金属鉱山株式会社 | Nickel composite hydroxide, method for producing the same, positive electrode active material for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery |
| CN109216687A (en) * | 2018-10-16 | 2019-01-15 | 桑顿新能源科技有限公司 | A kind of preparation method of monocrystalline trielement composite material and a kind of lithium ion battery |
| CN114613987B (en) * | 2022-03-22 | 2024-03-29 | 格林美（无锡）能源材料有限公司 | Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof |
-
2022
- 2022-03-22 CN CN202210283165.9A patent/CN114613987B/en active Active
- 2022-07-28 WO PCT/CN2022/108632 patent/WO2023178900A1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700845A (en) * | 2013-12-18 | 2014-04-02 | 江苏科捷锂电池有限公司 | Preparation method of concentration gradient distributed lithium, nickel, cobalt, manganese and oxygen ternary lithium battery cathode material |
| CN104241640A (en) * | 2014-10-10 | 2014-12-24 | 国家电网公司 | Lithium nickel-cobalt-aluminum positive electrode material, preparation method thereof and lithium ion battery |
| CN105226270A (en) * | 2015-10-22 | 2016-01-06 | 北京科技大学 | There is Li, Ni, Mn oxide positive electrode of nickel manganese concentration gradient and preparation method thereof |
| CN106207138A (en) * | 2016-09-20 | 2016-12-07 | 中国科学院化学研究所 | A kind of method for preparing anode material of lithium-ion battery and application thereof |
| CN111769277A (en) * | 2020-06-30 | 2020-10-13 | 中国科学院上海微系统与信息技术研究所 | Gradient single crystal high-nickel cathode material and preparation method thereof |
| CN112928253A (en) * | 2021-01-22 | 2021-06-08 | 厦门厦钨新能源材料股份有限公司 | Nickel-manganese-titanium composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 全浓度梯度高镍正极材料的可控制备及性能;张建 等;上海航天（中英文）;第37卷(第2期);第30-37页 * |
| 张建 等.全浓度梯度高镍正极材料的可控制备及性能.上海航天（中英文）.2020,第37卷(第2期),第30-37页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023178900A1 (en) | 2023-09-28 |
| CN114613987A (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114613987B (en) | Nickel cobalt lithium manganate gradient positive electrode material and preparation method thereof | |
| CN113955809B (en) | Nickel-cobalt-manganese-lithium aluminate positive electrode material with shell-core structure and preparation method thereof | |
| CN107275633B (en) | Gradient fluorine-doped ternary cathode material with low lattice stress and preparation method thereof | |
| CN111634958A (en) | Precursor for lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material | |
| CN113651373A (en) | Anode material with uniform porous structure and preparation method thereof | |
| CN111816877A (en) | High-nickel cobalt-free quaternary anode material and preparation method thereof | |
| CN107123792B (en) | Ternary cathode material with double-layer composite structure and preparation method thereof | |
| US11876209B2 (en) | Pre-lithiated lithium ion positive electrode material, and preparation method therefor and use thereof | |
| EP4047688A1 (en) | Lithium-manganese-rich material, preparation method for same, and applications thereof | |
| CN115196691A (en) | Nickel-iron-manganese ternary precursor for sodium ion battery and preparation method and application thereof | |
| EP4027408A1 (en) | Lithium-rich manganese-based material, preparation method therefor and application thereof | |
| CN113793927B (en) | Ternary cathode material of lithium ion battery and preparation method thereof | |
| CN114497527B (en) | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery | |
| CN115259244B (en) | Cobalt gradient high-nickel ternary positive electrode material, preparation method thereof and lithium ion battery | |
| CN115010190B (en) | High-entropy oxide positive electrode material and preparation method and application thereof | |
| WO2023246102A1 (en) | Hafnium-modified high-nickel layered oxide electrode material and preparation method therefor | |
| CN111082041B (en) | Lithium-rich multi-element positive electrode material, preparation method thereof, positive electrode and lithium ion power battery | |
| CN116230887A (en) | Precursor of positive electrode material of sodium ion battery, positive electrode material with Cu concentration gradient, preparation method and sodium ion battery | |
| CN116986649A (en) | Low-residual-alkali sodium-electricity positive electrode material, preparation method thereof and sodium-ion battery | |
| CN117080412A (en) | Sodium ion battery positive electrode material, preparation method, positive electrode plate and sodium ion battery | |
| CN111682174A (en) | Antimony-coated lithium battery positive electrode material and preparation method and application thereof | |
| CN114573050A (en) | Modified preparation method of ternary cathode material of lithium ion battery | |
| CN114937779B (en) | High-nickel monocrystal ternary positive electrode material for lithium ion battery and preparation method thereof | |
| CN113764671A (en) | Anode material of lithium ion battery | |
| CN111430710B (en) | Modified nickel cobalt lithium manganate ternary cathode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |