CN113793923A - Co-doped ternary positive electrode precursor, preparation method thereof, ternary positive electrode material and secondary battery - Google Patents
Co-doped ternary positive electrode precursor, preparation method thereof, ternary positive electrode material and secondary battery Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 title claims description 19
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 37
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 30
- 229910003616 NixCoyMn1−x−yCO3 Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 60
- 239000002245 particle Substances 0.000 claims description 55
- 239000010406 cathode material Substances 0.000 claims description 49
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 34
- 239000012266 salt solution Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 27
- 239000012716 precipitator Substances 0.000 claims description 25
- 238000000975 co-precipitation Methods 0.000 claims description 23
- 239000011572 manganese Substances 0.000 claims description 21
- -1 neodymium ions Chemical class 0.000 claims description 21
- 150000001206 Neodymium Chemical class 0.000 claims description 17
- 150000001868 cobalt Chemical class 0.000 claims description 17
- 159000000003 magnesium salts Chemical class 0.000 claims description 17
- 150000002696 manganese Chemical class 0.000 claims description 17
- 150000002815 nickel Chemical class 0.000 claims description 17
- 239000011775 sodium fluoride Substances 0.000 claims description 17
- 235000013024 sodium fluoride Nutrition 0.000 claims description 17
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 claims description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 229910001437 manganese ion Inorganic materials 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000011698 potassium fluoride Substances 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 3
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000010405 anode material Substances 0.000 abstract description 34
- 239000011737 fluorine Substances 0.000 abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 abstract description 27
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 239000000463 material Substances 0.000 description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 230000002829 reductive effect Effects 0.000 description 20
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 15
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 14
- 238000005245 sintering Methods 0.000 description 12
- 239000011164 primary particle Substances 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000012066 reaction slurry Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000005056 compaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- UTWHRPIUNFLOBE-UHFFFAOYSA-H neodymium(3+);tricarbonate Chemical compound [Nd+3].[Nd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O UTWHRPIUNFLOBE-UHFFFAOYSA-H 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the field of battery anode materials, and provides a co-doped ternary anode precursor and a preparation method thereof, a ternary anode material and a secondary battery. The general formula of the co-doped ternary positive electrode precursor is NixCoyMn1‑x‑yCO3·aMgF2·bNd2(CO3)3Wherein, the values of x, y, a and b satisfy: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02. The co-doped ternary cathode precursor provided by the application is doped with fluorine, magnesium and neodymium. Because fluorine, magnesium and neodymium are doped in the precursor, doping atoms can realize doping at an atomic level, and the doping uniformity of doping elements is improved.
Description
Technical Field
The application belongs to a battery anode material, and particularly relates to a co-doped ternary anode precursor and a preparation method thereof, a ternary anode material and a secondary battery.
Background
The ternary anode material has the advantages of low cost, large discharge capacity, stable structure and the like, and becomes one of the novel lithium ion battery anode materials with the most development prospect at present. The surface of the ternary cathode material is contacted with electrolyte to realize cations such as Li+Is transmitted. Doping F in positive electrode material-Fluorine can partially replace oxygen during cell cyclingCan reduce oxygen release, thereby reducing side reaction of the electrolyte, inhibiting gas generation and improving the safety performance of the battery. But now F-The doping is carried out in the anode sintering stage, the doping uniformity is poor, and the structural stability of the ternary anode material is influenced.
Disclosure of Invention
The application aims to provide a co-doped ternary cathode precursor and a preparation method thereof, a ternary cathode material and a secondary battery, and aims to solve the problem that the structural stability of the ternary cathode material is influenced due to poor doping uniformity of the existing doped ternary cathode precursor.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the application provides a codoped ternary positive electrode precursor with a general formula of NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3Wherein, the values of x, y, a and b satisfy: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
The co-doped ternary cathode precursor provided by the application is doped with fluorine, magnesium and neodymium. Because fluorine, magnesium and neodymium are doped in the precursor, doping atoms can realize doping at an atomic level, and the doping uniformity of doping elements in the corresponding anode material is improved. On the basis, the fluorine atoms replace part of oxygen atoms in the corresponding anode material, and the corresponding anode material can reduce oxygen release in the circulating process, so that the side reaction of the electrolyte is reduced, and the circulating performance of the battery is finally improved; meanwhile, the neodymium element introduced into the ternary cathode precursor can also improve the structural stability of the corresponding ternary cathode material, and further improve the cycle performance of the obtained ternary cathode material. In addition, fluorine and magnesium form magnesium fluoride, and the magnesium fluoride is used as a fluxing agent to reduce the sintering temperature of the cathode material and reduce the size of primary particles, so that the rate capability of the cathode material is improved.
As an implementation mode of the co-doping ternary anode precursor, the values of x, y, a and b satisfy the following conditions: x is more than or equal to 0.5 and less than 1, y is more than or equal to 0.05 and less than or equal to 0.2, a is more than or equal to 0.0005 and less than or equal to 0.02, and b is more than or equal to 0.0005 and less than or equal to 0.004. In the co-doped ternary anode precursor obtained under the condition, fluorine, magnesium and neodymium are doped in the ternary anode precursor in proper content, so that the structural stability and the rate capability of the corresponding anode material can be improved, the capacity of the corresponding anode material cannot be influenced due to overhigh doping amount, and the cycle performance of the corresponding battery is improved.
As an implementation of the codoped ternary positive precursor of the present application, the precursor is
Ni0.5Co0.2Mn0.3CO3·0.0025MgF2·0.001Nd2(CO3)3、
Ni0.6Co0.2Mn0.2CO3·0.005MgF2·0.002Nd2(CO3)3、
Ni0.7Co0.15Mn0.15CO3·0.01MgF2·0.003Nd2(CO3)3、
Ni0.85Co0.1Mn0.05CO3·0.02MgF2·0.004Nd2(CO3)3At least one of (1). The precursor has good structural stability and rate capability corresponding to the anode material, can improve the cycle performance of the battery, and can keep the high capacity of the corresponding anode material.
The second aspect of the application provides a preparation method of a co-doped ternary cathode precursor, which comprises the following steps:
preparing a metal salt solution containing nickel salt, cobalt salt, manganese salt, magnesium salt and neodymium salt, a fluoride solution and a precipitator;
adding the metal salt solution, the fluoride solution and the precipitator into a reaction kettle, and carrying out coprecipitation chemical reaction under protective atmosphere to prepare the co-doped ternary cathode precursor, wherein the general formula of the precursor is NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3Wherein, the values of x, y, a and b satisfy: x is more than 0 and less than 1,0<y<1,0.0003<a<0.02,0.0001<b<0.02。
according to the preparation method of the co-doped ternary cathode precursor, the main metal salt, the doping metal salt and the fluoride solution are mixed and co-precipitated to realize the doping of fluorine, magnesium and neodymium, and the method can realize the doping of fluorine, magnesium and neodymium at an atomic level, so that the doping uniformity of doping atoms is improved. After the codoped ternary positive electrode precursor is synthesized into a corresponding positive electrode material, fluorine atoms replace part of oxygen atoms, and oxygen release can be reduced in the circulation process of the corresponding positive electrode material, so that the side reaction of electrolyte is reduced, and the circulation performance of the battery is finally improved; meanwhile, the neodymium element introduced into the ternary anode precursor can also improve the structural stability of the corresponding ternary anode material, and further improve the cycle performance of the corresponding ternary anode material. In addition, magnesium fluoride is formed in the doping process of fluorine and magnesium, and the magnesium fluoride is used as a fluxing agent to reduce the sintering temperature of the cathode material and reduce the size of primary particles, so that the rate capability of the cathode material is improved.
As an implementation mode of the preparation method of the co-doped ternary cathode precursor, the total concentration of nickel ions, cobalt ions and manganese ions in the metal salt solution is 0.5-2.0 mol/L, and the concentration of the fluoride solution is 0.5-2.0 mol/L. Correspondingly, the concentration of magnesium ions in the metal salt solution is a times of the total concentration of nickel ions, cobalt ions and manganese ions, and the concentration of neodymium ions is 2b times of the total concentration of nickel ions, cobalt ions and manganese ions. After the ternary positive electrode precursor formed under the condition is synthesized into the corresponding positive electrode material, the structural stability and the rate capability of the corresponding positive electrode material can be improved, the capacity of the positive electrode material can be kept, and the cycle performance of the corresponding battery can be improved.
As an implementation mode of the preparation method of the co-doped ternary cathode precursor, the precipitator is a precipitator solution, and the concentration of the precipitator in the precipitator solution is 0.5-10 mol/L. The concentration of the precipitant solution is in the range, the coprecipitation rate of the doped ternary anode precursor can be effectively controlled, and the uniformity of the particle size of the doped ternary anode precursor is improved.
As an implementation of the preparation method of the co-doped ternary cathode precursor, the nickel salt is at least one selected from sulfate, nitrate, chloride and acetate of nickel;
the cobalt salt is selected from at least one of sulfate, nitrate, chloride and acetate of cobalt;
the manganese salt is selected from at least one of sulfate, nitrate, chloride and acetate of manganese;
the magnesium salt is selected from at least one of sulfate, nitrate, chloride and acetate of magnesium;
the neodymium salt is selected from at least one of sulfate, nitrate, chloride and acetate of neodymium;
the fluoride in the fluoride solution is selected from sodium fluoride or potassium fluoride.
The metal salt has good solubility, and can be uniformly co-precipitated with anions in an ionic state after being introduced into the reaction kettle to obtain the co-doped ternary cathode precursor. Likewise, sodium fluoride or potassium fluoride can provide fluoride ions in the reaction system, and the fluoride ions are combined with metal ions in the metal salt solution and co-precipitated to form the co-doped ternary cathode precursor. Particularly, in the co-doping process, fluorine ions provided by the fluoride solution and magnesium ions provided by the metal solution are combined to form magnesium fluoride, so that the sintering temperature of the anode material is favorably reduced, the size of primary particles is reduced, and the rate capability of the corresponding anode material is improved.
As an implementation manner of the preparation method of the co-doped ternary cathode precursor, the co-precipitation chemical reaction is carried out under the protective atmosphere to prepare the co-doped ternary cathode precursor, which comprises the following steps:
and (3) carrying out coprecipitation chemical reaction under a protective atmosphere, and finishing the reaction after the average particle size of the slurry in the reaction kettle reaches a preset particle size to prepare the co-doped ternary cathode precursor.
By monitoring the average particle size of the slurry in the reaction kettle, the co-doped ternary cathode precursor with the particle size within an expected range can be prepared, so that the improvement of the particle size uniformity of the ternary cathode material is facilitated.
As an implementation mode of the preparation method of the co-doped ternary cathode precursor, the preset particle size is 3-16 micrometers. Under the condition, the particle size of the co-doped ternary cathode precursor material is in a proper range, the particle size of the correspondingly obtained ternary cathode material is proper, the compaction rate is high, and the material is not easy to break.
As an implementation manner of the preparation method of the co-doped ternary cathode precursor, the precipitant is at least one of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate.
As an implementation mode of the preparation method of the co-doped ternary cathode precursor, the reaction temperature of the co-precipitation chemical reaction is 25-65 ℃. Under the temperature condition, metal ions in the metal salt solution react with precipitator anions and fluorine ions in fluoride in a reaction system, and co-precipitate to form the co-doped ternary cathode precursor.
The third aspect of the application provides a co-doped ternary cathode material, wherein the general formula of the cathode material is LiNixCoyMn1-x-yO2·aMgF2·bNd2O3And the cathode material is prepared from the codoped ternary cathode precursor in the first aspect or the codoped ternary cathode precursor prepared by the method in the second aspect and lithium, wherein the values of x, y, a and b satisfy the following conditions: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
The application provides a codoped ternary cathode material, because fluorine, magnesium and neodymium realize the doping in the precursor, consequently, doping atom can realize the doping of atomic level, has improved doping element's doping homogeneity. On the basis, fluorine and neodymium elements act together to improve the structural stability of the corresponding ternary cathode material and further improve the cycle performance of the obtained ternary cathode material. In addition, magnesium fluoride in the co-doped ternary cathode precursor is used as a fluxing agent, so that the sintering temperature of the cathode material can be reduced, and the size of primary particles is reduced, so that the rate performance of the cathode material is improved.
A fourth aspect of the present application provides a secondary battery comprising the co-doped ternary cathode material according to the third aspect.
The secondary battery provided by the application contains the co-doped ternary cathode material, so that the structural stability of a ternary precursor can be improved, and the cycle performance of the secondary battery is further improved.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In a first aspect, an embodiment of the present application provides a co-doped ternary positive electrode precursor, where the general formula of the precursor is NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3Wherein, the values of x, y, a and b satisfy: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
The ternary anode precursor is a precursor material of a ternary anode material, and the ternary anode material is matched with lithium to obtain the ternary anode material. In the embodiment of the application, the ternary positive electrode precursor is a fluorine, magnesium and neodymium doped nickel-cobalt-manganese ternary precursor. Because fluorine, magnesium and neodymium are doped in the precursor, doping atoms can realize doping at an atomic level, and the doping uniformity of doping elements is improved.
The doped fluorine can replace part of oxygen atoms in the corresponding anode material, and the corresponding anode material can reduce oxygen release in the circulation process, so that the side reaction of the electrolyte is reduced, and the circulation performance of the battery is finally improved.
In the present embodiment, the doped magnesium and the doped fluorine form magnesium fluoride. In the process of sintering the codoped ternary anode precursor with lithium, magnesium fluoride as a fluxing agent can reduce the sintering temperature of the anode material and reduce the size of primary particles, thereby improving the rate capability of the anode material.
In the embodiment of the application, the relative molar weight of the nickel-cobalt-manganese ternary precursor is 1, the relative molar weight of the doped fluorine is 2a, the relative molar weight of the doped magnesium is a, and the value of a satisfies the following conditions: 0.0003 < a < 0.02. In this case, fluorine and magnesium can be doped effectively, and the influence of fluorine and magnesium doping on the capacity of the positive electrode material can be reduced by controlling the contents within the above ranges.
In the embodiment of the application, the doped neodymium is fused into the corresponding ternary cathode material by trivalent ions, so that the structural stability of the cathode material can be improved, and the cycle performance of the obtained ternary cathode material is further improved. And (2) taking the relative molar weight of the nickel-cobalt-manganese ternary precursor as 1, taking the relative molar weight of the doped neodymium as 2b, wherein the value of b satisfies the following conditions: b is more than 0.0001 and less than 0.02. In this case, the doped neodymium can effectively exert the above-described effects, and at the same time, the influence of neodymium on the capacity of the anode material can be reduced by controlling the neodymium content within the above-described range.
In one possible implementation mode, the values of x and y in the nickel-cobalt-manganese ternary precursor satisfy the following condition: x is more than or equal to 0.5 and less than 1, y is more than or equal to 0.05 and less than or equal to 0.2, and the contents of fluorine, magnesium and neodymium doped in the nickel-cobalt-manganese ternary precursor, namely the values of a and b, meet the following requirements: a is more than or equal to 0.0005 and less than or equal to 0.02, and b is more than or equal to 0.0005 and less than or equal to 0.004. In the co-doped ternary anode precursor obtained under the condition, fluorine, magnesium and neodymium are doped in the corresponding ternary anode material in proper content, so that the structural stability and the rate capability of the corresponding anode material can be improved, the capacity of the anode material cannot be influenced due to overhigh doping amount, and the cycle performance of the corresponding battery is improved.
In one possible embodiment, the co-doped ternary cathode precursor is
Ni0.5Co0.2Mn0.3CO3·0.0025MgF2·0.001Nd2(CO3)3、
Ni0.6Co0.2Mn0.2CO3·0.005MgF2·0.002Nd2(CO3)3、
Ni0.7Co0.15Mn0.15CO3·0.01MgF2·0.003Nd2(CO3)3、
Ni0.85Co0.1Mn0.05CO3·0.02MgF2·0.004Nd2(CO3)3At least one of (1). The precursor has good structural stability and rate capability corresponding to the anode material, can improve the cycle performance of the battery, and can keep the high capacity of the corresponding anode material.
In one possible implementation mode, the particle size of the co-doped ternary positive electrode precursor is 3-16 mu m. Under the condition, the particle size of the co-doped ternary cathode precursor material is in a proper range, the particle size of the correspondingly obtained ternary cathode material is proper, the compaction rate is high, and the material is not easy to break. If the particle size of the co-doped ternary cathode precursor particles is too small, the material synthesis difficulty is high, the material is difficult to synthesize by a common process, and the lower the compaction rate of the material is, the more fine material powder is; if the particle size of the co-doped ternary positive precursor particles is too large, the particles are easy to be too large in the process, and the particles are easy to be broken, so that the performance of the battery is influenced.
The codoped ternary cathode precursor provided by the embodiment of the application can be prepared by the following method.
In a second aspect, an embodiment of the present application provides a method for preparing a co-doped ternary cathode precursor, including the following steps:
s01, preparing a metal salt solution containing nickel salt, cobalt salt, manganese salt, magnesium salt and neodymium salt, a fluoride solution and a precipitator.
In the step, a metal salt solution provides cations for preparing a co-doped ternary cathode precursor, specifically, nickel salt provides nickel ions, cobalt salt provides cobalt ions, manganese salt provides manganese ions, magnesium salt provides magnesium ions, and neodymium salt provides trivalent neodymium ions.
In some possible embodiments, a metal salt solution comprising a nickel salt, a cobalt salt, a manganese salt, a magnesium salt, a neodymium salt is configured, comprising: adding nickel salt, cobalt salt, manganese salt, magnesium salt and neodymium salt into deionized water according to a preset proportion and a preset total content of metal ions, and mixing to form a metal salt solution with a preset concentration. Wherein, nickel salt, cobalt salt and manganese salt are main metal salts, and magnesium salt and neodymium salt are doped metal salts.
Preparing nickel salt, cobalt salt and manganese salt of metal salt solution, and selecting common nickel salt, cobalt salt and manganese salt for preparing the nickel-cobalt-manganese ternary precursor. In some possible embodiments, the nickel salt is selected from at least one of a sulfate, a nitrate, a chloride, and an acetate salt of nickel; the cobalt salt is at least one selected from sulfate, nitrate, chloride and acetate of cobalt; the manganese salt is selected from at least one of sulfate, nitrate, chloride and acetate of manganese. The metal salt solution is formulated with magnesium salts and neodymium salts selected to have good solubility in the metal salt solution, and illustratively, the magnesium salts and the neodymium salts are selected to have good water solubility. In one possible embodiment, the magnesium salt is selected from at least one of a sulfate, a nitrate, a chloride, and an acetate salt of magnesium; the neodymium salt is selected from at least one of sulfate, nitrate, chloride and acetate of neodymium.
The metal salt has good solubility, and can be uniformly co-precipitated with anions in an ionic state after being introduced into the reaction kettle to obtain the co-doped ternary cathode precursor.
In some possible embodiments, the total concentration of nickel ions, cobalt ions, and manganese ions (also referred to as "total concentration of nickel-cobalt-manganese metal ions") in the metal salt solution is 0.5-2.0 mol/L, and the concentration of the fluoride solution is 0.5-2.0 mol/L. Correspondingly, the concentration of magnesium ions in the metal salt solution is a times of the total concentration of nickel ions, cobalt ions and manganese ions, and the concentration of neodymium ions is 2b times of the total concentration of nickel ions, cobalt ions and manganese ions. After the ternary positive electrode precursor formed under the condition is synthesized into the corresponding positive electrode material, the structural stability and the rate capability of the corresponding positive electrode material can be improved, the capacity of the positive electrode material can be kept, and the cycle performance of the corresponding battery can be improved. In the examples of the present application, when a metal salt solution containing a nickel salt, a cobalt salt, a manganese salt, a magnesium salt, and a neodymium salt is prepared, the order of addition of the respective salts is not particularly limited. For example, nickel salt, cobalt salt and manganese salt can be added into deionized water, and then magnesium salt and neodymium salt are added for mixing treatment; or adding magnesium salt and neodymium salt into deionized water, and then adding nickel salt, cobalt salt and manganese salt. Of course, the manner of addition is not limited thereto.
In the embodiment of the application, the fluoride solution provides fluoride ions for preparing the co-doped ternary cathode precursor. In some possible embodiments, a fluoride solution is configured comprising: adding fluoride salt into deionized water according to a preset content, and mixing to form a fluoride solution with a preset concentration.
In some possible embodiments, the fluoride in the fluoride solution is selected from sodium fluoride or potassium fluoride. The sodium fluoride or the potassium fluoride can provide fluoride ions in a reaction system, and the fluoride ions are combined with metal ions in a metal salt solution after being mixed with the metal salt solution to form a co-doped ternary cathode precursor through coprecipitation. In particular, in the co-doping process, fluoride ions provided by the fluoride solution and magnesium ions provided by the metal solution are combined to form magnesium fluoride, so that the sintering temperature of the cathode material is favorably reduced, the size of primary particles is reduced, and the uniformity of the primary particles is improved.
In the embodiment of the application, the precipitator is used for promoting the conversion of nickel salt, cobalt salt, manganese salt, magnesium salt and neodymium salt into metal compound precipitate and the metal compound precipitate are converted into the co-doped ternary cathode precursor. In one possible embodiment, the precipitant is at least one of sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate. The precipitant can convert nickel salt, cobalt salt, and manganese salt into nickel carbonate, cobalt carbonate, and manganese carbonate precipitate, magnesium salt into magnesium fluoride precipitate, neodymium salt into neodymium carbonate precipitate, and NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3。
In some possible embodiments, the precipitant is a precipitant solution, and the concentration of the precipitant in the precipitant solution is 0.5 to 10 mol/L. The concentration of the precipitant solution is in the range, the coprecipitation rate of the doped ternary anode precursor can be effectively controlled, and the uniformity of the particle size of the doped ternary anode precursor is improved. If the concentration of the precipitant is too high, the particle growth speed is too fast, and the particle size of the co-doped ternary cathode precursor is not easy to control.
S02, adding a metal salt solution, a fluoride solution and a precipitator into a reaction kettle, and carrying out coprecipitation chemical reaction under a protective atmosphere to prepare a co-doped ternary cathode precursor, wherein the general formula of the precursor is NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3Wherein, the values of x, y, a and b satisfy: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
In the step, a metal salt solution, a fluoride solution and a precipitator are fed into a reaction kettle, and a coprecipitation chemical reaction is controlled by regulating the contents of the metal salt solution, the fluoride solution and the precipitator to generate a ternary anode precursor NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3。
In one possible implementation, the co-doped ternary positive electrode precursor is generated by continuously adding a metal salt solution, a fluoride solution and a precipitant into a reaction kettle. The process can monitor and adjust the reaction process by testing the temperature of the reaction liquid in the reaction kettle or the particle size of the slurry, and stop feeding after the particle size of the synthesized co-doped ternary cathode precursor particles meets the requirement.
In the embodiment of the application, the coprecipitation chemical reaction is carried out in the protective atmosphere, and the protective atmosphere can prevent air from being introduced into a reaction system, so that other side reactions are avoided. Wherein the inert atmosphere comprises one of a nitrogen atmosphere and an inert gas atmosphere. Illustratively, the inert gas is helium, neon, argon, krypton, or xenon.
In one possible implementation, a co-precipitation chemical reaction occurs under a protective atmosphere to produce a co-doped ternary positive precursor, including: and (3) carrying out coprecipitation chemical reaction under the protective atmosphere, and finishing the reaction after the average particle size of the slurry in the reaction kettle reaches a preset particle size to prepare the co-doped ternary cathode precursor. By monitoring the average particle size of the slurry in the reaction kettle, the co-doped ternary cathode precursor with the particle size within an expected range can be prepared. Illustratively, the average particle size of the slurry in the reaction kettle is measured every hour, and the reaction is ended after the average particle size of the slurry in the reaction kettle reaches a preset particle size.
In one possible implementation, the predetermined particle size is 3 to 16 μm. In this case, Ni is controlledxCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3The particle size of the precursor is 3-16 mu m, so that the phenomenon of fine powder caused by undersize particles can be reduced, the phenomenon of particle breakage caused by oversize particles can also be reduced, and after the co-doped ternary positive electrode precursor particles are converted into the ternary positive electrode material, the particle size is appropriate, the compaction rate is high, the particles are not easy to break, and the ternary positive electrode material can give consideration to compaction and rate capability.
In one possible implementation mode, the reaction temperature of the coprecipitation chemical reaction is 25-65 ℃. Under the temperature condition, metal ions in the metal salt solution react with precipitator anions and fluoride ions in fluoride in a reaction system, and co-precipitate to form the co-doped ternary cathode precursor. If the heating temperature is too high, the reaction speed of the coprecipitation chemical reaction is too high, large-particle co-doped ternary anode precursors are generated, and the spherical crack is easy to occur.
In some possible implementations, after the reaction is finished, the method further includes: the reaction solution is sequentially aged, filtered, washed and dried to finally obtain the general formula of NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3Co-doped with the ternary precursor.
According to the preparation method of the co-doped ternary cathode precursor, the main metal salt, the doping metal salt and the fluoride solution are mixed and co-precipitated to realize the doping of fluorine, magnesium and neodymium, and the method can realize the doping of fluorine, magnesium and neodymium at an atomic level, so that the doping uniformity of doping atoms is improved. After the corresponding anode material is synthesized, fluorine atoms replace part of oxygen atoms, so that oxygen release in the circulation process of the corresponding anode material can be reduced, side reactions of electrolyte in the circulation process are reduced, and the circulation performance of the battery is finally improved; meanwhile, the neodymium element introduced into the ternary cathode precursor can also improve the structural stability of the corresponding ternary cathode material, and further improve the cycle performance of the obtained ternary cathode material. In addition, magnesium fluoride is formed in the doping process of fluorine and magnesium, and the magnesium fluoride is used as a fluxing agent to reduce the sintering temperature of the cathode material and reduce the size of primary particles, so that the rate capability of the cathode material is improved.
In a third aspect, an embodiment of the present application provides a co-doped ternary cathode material, where the general formula of the co-doped ternary cathode material is LiNixCoyMn1-x-yO2·aMgF2·bNd2O3And the codoped ternary cathode material is prepared from the codoped ternary cathode precursor of the first aspect or the codoped ternary cathode precursor prepared by the method of the second aspect and lithiumThe preparation method is characterized in that the values of x and y meet the following requirements: x is more than 0 and less than 1, y is more than 0 and less than 1, and the values of a and b meet the following conditions: a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
The codoped ternary cathode material provided by the embodiment of the application has the advantages that doping of fluorine, magnesium and neodymium is realized in the precursor, so that doping atoms can realize doping at an atomic level, and the doping uniformity of doping elements is improved. On the basis, fluorine atoms and neodymium elements act together to improve the structural stability of the corresponding ternary cathode material and further improve the cycle performance of the obtained ternary cathode material. In addition, magnesium fluoride in the co-doped ternary cathode precursor is used as a fluxing agent, so that the sintering temperature of the cathode material can be reduced, and the size of primary particles is reduced, so that the rate performance of the cathode material is improved.
The co-doping of the ternary cathode precursor provided in the embodiments of the present application is as described above, and for the sake of brevity, the description is omitted here.
In one possible implementation manner, the co-doped ternary positive electrode precursor and a lithium source for providing lithium are calcined to promote the lithium to be rapidly diffused into the co-doped ternary positive electrode precursor crystal, so as to prepare the ternary positive electrode material. The magnesium fluoride in the co-doped ternary positive electrode precursor can reduce the sintering temperature during calcination, thereby reducing the size of primary particles and improving the rate capability of the positive electrode material.
In a fourth aspect, embodiments of the present application provide a secondary battery including the co-doped ternary cathode material of the third aspect.
The secondary battery provided by the embodiment of the application has better structural stability and better cycle performance due to the fact that the secondary battery contains the co-doped ternary cathode material.
The following description will be given with reference to specific examples.
Example 1
Ni0.5Co0.2Mn0.3CO3·0.0025MgF2·0.001Nd2(CO3)3The preparation method of the ternary positive electrode precursor material comprises the following steps:
adding sulfates of nickel, cobalt, manganese, magnesium and neodymium into deionized water according to a stoichiometric ratio, wherein the total concentration of nickel, cobalt and manganese metal ions is 2mol/L, adding sodium fluoride into the deionized water to prepare a sodium fluoride solution with the concentration of 0.5mol/L, and adding sodium carbonate into the deionized water to prepare a precipitator solution with the concentration of 2 mol/L;
adding a metal salt solution, a sodium fluoride solution and a precipitator solution into a reaction kettle according to a stoichiometric ratio by a metering pump, carrying out coprecipitation chemical reaction, testing the particle size of reaction slurry every hour, stopping feeding when the particle size in the slurry reaches 10.5 microns, and aging for 10 hours;
filtering, washing and drying the materials in the reaction kettle to obtain the required co-doped ternary precursor material Ni0.5Co0.2Mn0.3CO3·0.0025MgF2·0.001Nd2(CO3)3。
Example 2
Ni0.6Co0.2Mn0.2CO3·0.005MgF2·0.002Nd2(CO3)3The preparation method of the ternary positive electrode precursor material comprises the following steps:
adding chlorides of nickel, cobalt, manganese, magnesium and neodymium into deionized water according to a stoichiometric ratio to prepare a metal ion solution with the total metal ion concentration of 1.5mol/L, adding sodium fluoride into the deionized water to prepare a sodium fluoride solution with the concentration of 0.8mol/L, and adding ammonium carbonate into the deionized water to prepare a precipitator solution with the concentration of 5 mol/L;
adding a main metal ion solution, a sodium fluoride solution and a precipitator solution into a reaction kettle according to a stoichiometric ratio through a metering pump, carrying out coprecipitation chemical reaction, testing the particle size of reaction slurry every hour, stopping feeding when the particle size in the slurry reaches 10 micrometers, and aging for 12 hours;
filtering, washing and drying the materials in the reaction kettle to obtain the ternary precursor Ni to be co-doped0.6Co0.2Mn0.2CO3·0.005MgF2·0.002Nd2(CO3)3。
Example 3
Ni0.7Co0.15Mn0.15CO3·0.01MgF2·0.003Nd2(CO3)3The preparation method of the ternary positive electrode precursor material comprises the following steps:
adding nitrates of nickel, cobalt, manganese, magnesium and neodymium into deionized water according to a stoichiometric ratio to prepare a metal salt solution with the total concentration of metal ions being 1.8mol/L, adding potassium fluoride into the deionized water to prepare a potassium fluoride solution with the concentration being 1mol/L, and adding ammonium bicarbonate into the deionized water to prepare a precipitator solution with the concentration being 4 mol/L;
adding a main metal salt solution, a potassium fluoride solution and a precipitator solution into a reaction kettle according to a stoichiometric ratio through a metering pump, carrying out coprecipitation chemical reaction, testing the particle size of reaction slurry every hour, stopping feeding when the particle size in the slurry reaches 11 microns, and aging for 14 hours;
filtering, washing and drying the materials in the reaction kettle to obtain the ternary precursor Ni to be co-doped0.7Co0.15Mn0.15CO3·0.01MgF2·0.003Nd2(CO3)3。
Example 4
Ni0.85Co0.1Mn0.05CO3·0.02MgF2·0.004Nd2(CO3)3The preparation method of the ternary positive electrode precursor material comprises the following steps:
adding acetates of nickel, cobalt, manganese, magnesium and neodymium into deionized water according to a stoichiometric ratio to prepare a metal salt solution with the total concentration of metal ions of 1.7mol/L, adding sodium fluoride into the deionized water to prepare a sodium fluoride solution with the concentration of 1.5mol/L, and adding ammonium carbonate into the deionized water to prepare a precipitator solution with the concentration of 6 mol/L;
adding a main metal salt solution, a sodium fluoride solution and a precipitator solution into a reaction kettle according to a stoichiometric ratio through a metering pump, carrying out coprecipitation chemical reaction, testing the particle size of reaction slurry every hour, stopping feeding when the particle size in the slurry reaches 11.5um, and aging for 15 hours;
filtering and washing the materials in the reaction kettleDrying to obtain the ternary precursor Ni to be codoped0.85Co0.1Mn0.05CO3·0.02MgF2·0.004Nd2(CO3)3。
Comparative example 1
Ni0.5Co0.2Mn0.3CO3The preparation method of the conventional ternary cathode precursor material comprises the following steps:
adding sulfates of nickel, cobalt and manganese into a deionized water solution, wherein the ratio of nickel, cobalt and manganese is 5:2:3, preparing a salt solution with metal ion concentration of 1.5mol/L, and preparing a 4mol/L ammonium carbonate precipitant solution;
adding a nickel-cobalt-manganese sulfate solution and an ammonium carbonate solution into a reaction kettle according to a stoichiometric ratio through a metering pump to perform coprecipitation chemical reaction, testing the particle size of reaction slurry every hour, stopping feeding when the particle size in the slurry reaches 10 mu m, and aging for 10 hours;
filtering, washing and drying the materials in the reaction kettle to obtain the required ternary precursor Ni0.5Co0.2Mn0.3CO3。
Comparative example 2
Ni0.5Co0.2Mn0.3CO3·0.0005MgF2The preparation method of the ternary positive electrode precursor material comprises the following steps:
adding sulfates of nickel, cobalt, manganese and magnesium into deionized water according to a stoichiometric ratio, wherein the total concentration of nickel, cobalt and manganese metal ions is 2mol/L, adding sodium fluoride into the deionized water to prepare a sodium fluoride solution with the concentration of 0.5mol/L, and adding sodium carbonate into the deionized water to prepare a precipitator solution with the concentration of 2 mol/L;
adding a metal salt solution, a sodium fluoride solution and a precipitator solution into a reaction kettle according to a stoichiometric ratio by a metering pump, carrying out coprecipitation chemical reaction, testing the particle size of reaction slurry every hour, stopping feeding when the particle size in the slurry reaches 10.5 microns, and aging for 10 hours;
filtering, washing and drying the materials in the reaction kettle to obtain the required co-doped ternary precursor material Ni0.5Co0.2Mn0.3CO3·0.0005MgF2。
Comparative example 3
LiNi0.5Co0.2Mn0.3O2·0.0005MgF2·0.0005Nd2O3The preparation method of the ternary cathode material comprises the following steps:
mixing Li2CO3、Ni0.5Co0.2Mn0.3CO3、MgF2、Nd2O3Weighing the materials according to the molar ratio of 0.54:1:0.0005:0.0005, uniformly mixing, and calcining at 920 ℃ for 13 hours to obtain the ternary cathode material LiNi0.5Co0.2Mn0.3O2·0.0005MgF2·0.0005Nd2O3。
Respectively weighing and uniformly mixing lithium carbonate and the fluorine magnesium neodymium co-doped ternary cathode precursor obtained in the embodiment 1-2 according to the Li to M (nickel-cobalt-manganese transition metal) molar ratio of 1.08, and respectively calcining at 920 ℃ and 875 ℃ for 13 hours to obtain the fluorine magnesium neodymium co-doped ternary cathode material with the corresponding ratio. And (2) respectively weighing and uniformly mixing lithium hydroxide and the fluorine magnesium neodymium co-doped ternary cathode precursor obtained in the embodiment 3-4 according to the Li to M (nickel-cobalt-manganese transition metal) molar ratio of 1.06, and respectively calcining at the temperature of 800 ℃ and the temperature of 760 ℃ for 13 hours to obtain the fluorine magnesium neodymium co-doped ternary cathode material with the corresponding ratio. Respectively weighing and uniformly mixing lithium carbonate and the nickel-cobalt-manganese precursor obtained in the comparative examples 1-2 according to the molar ratio of Li to M (nickel-cobalt-manganese transition metal) of 1.08, and respectively calcining at 950 ℃ and 920 ℃ for 13 hours to obtain the nickel-cobalt-manganese-lithium ternary cathode material with the corresponding ratio.
The ternary positive electrode materials corresponding to examples 1 to 4 and comparative examples 1 to 3 were mixed and slurried according to the ternary positive electrode material SP: PVDF: 96:2:2, and the slurry was coated on an aluminum foil, controlled to have the same areal density, and die-cut after baking, to obtain a positive electrode sheet. And (3) preparing the button lithium ion battery by using the diaphragm, the positive plate corresponding to the examples 1-4 and the comparative examples 1-3 and the lithium metal plate. The performance of the button lithium ion battery is detected by the following method:
the first gram capacity discharge was measured under the conditions of 3-4.3V, 0.1C/0.1C charge and discharge for each of the above-mentioned charging points, and the rate performance, i.e., 2C/0.1C, was compared between the conditions of 0.5C/2C charge and discharge and 0.1C/0.1C charge and discharge, and then the cycle performance was compared for 100 weeks after 1C/1C cycle, and the test results are shown in Table 1 below.
TABLE 1
As can be seen from table 1, the cathode material formed by the co-doped ternary cathode precursor material prepared in examples 1 to 4 of the present application has more excellent rate and cycle performance. This is due to: according to the embodiment of the application, the magnesium neodymium fluoride is doped in the nickel-cobalt-manganese anode precursor, so that the structural stability of the ternary anode material is improved, and the cycle performance of the battery is further improved; and the sintering temperature of the ternary positive electrode precursor doped with fluorine, magnesium and neodymium is reduced, so that the primary particles of the correspondingly obtained positive electrode material are reduced, and the rate capability of the battery is improved.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed.
Claims (11)
1. The co-doped ternary positive electrode precursor is characterized in that the general formula of the precursor is NixCoyMn1-x-yCO3·aMgF2·bNd2(CO3)3Wherein, the values of x, y, a and b satisfy: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
2. The co-doped ternary positive precursor according to claim 1, wherein x, y, a, and b have values satisfying: x is more than or equal to 0.5 and less than 1, y is more than or equal to 0.05 and less than or equal to 0.2, a is more than or equal to 0.0005 and less than or equal to 0.02, and b is more than or equal to 0.0005 and less than or equal to 0.004.
3. The co-doped ternary positive precursor according to claim 1 or 2, wherein the precursor is Ni0.5Co0.2Mn0.3CO3·0.0025MgF2·0.001Nd2(CO3)3、Ni0.6Co0.2Mn0.2CO3·0.005MgF2·0.002Nd2(CO3)3、Ni0.7Co0.15Mn0.15CO3·0.01MgF2·0.003Nd2(CO3)3、Ni0.85Co0.1Mn0.05CO3·0.02MgF2·0.004Nd2(CO3)3At least one of (1).
4. A preparation method of a co-doped ternary cathode precursor is characterized by comprising the following steps:
preparing a metal salt solution containing nickel salt, cobalt salt, manganese salt, magnesium salt and neodymium salt, a fluoride solution and a precipitator;
adding the metal salt solution, the fluoride solution and the precipitator into a reaction kettle, and carrying out coprecipitation chemical reaction under protective atmosphere to prepare the co-doped ternary cathode precursor, wherein the general formula of the precursor is NixCoyMn1-x- yCO3·aMgF2·bNd2(CO3)3Wherein, the values of x, y, a and b satisfy: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
5. The preparation method of the co-doped ternary cathode precursor according to claim 4, wherein in the metal salt solution, the total concentration of nickel ions, cobalt ions and manganese ions is 0.5-2.0 mol/L, the concentration of magnesium ions is a times of the total concentration of nickel ions, cobalt ions and manganese ions, the concentration of neodymium ions is 2b times of the total concentration of nickel ions, cobalt ions and manganese ions, and the concentration of the fluoride solution is 0.5-2.0 mol/L; and/or
The precipitant is a precipitant solution, and the concentration of the precipitant in the precipitant solution is 0.5-10 mol/L.
6. The method according to claim 4, wherein the nickel salt is at least one selected from the group consisting of a sulfate, a nitrate, an acetate, and a chloride of nickel;
the cobalt salt is selected from at least one of sulfate, nitrate, acetate and chloride of cobalt;
the manganese salt is selected from at least one of sulfate, nitrate, acetate and chloride of manganese;
the magnesium salt is selected from at least one of sulfate, nitrate, acetate and chloride of magnesium;
the neodymium salt is selected from at least one of sulfate, nitrate, acetate and chloride of neodymium;
the fluoride in the fluoride solution is selected from sodium fluoride or potassium fluoride.
7. The preparation method of the co-doped ternary cathode precursor according to any one of claims 4 to 6, wherein in the step of preparing the co-doped ternary cathode precursor through a coprecipitation chemical reaction under a protective atmosphere, the reaction is terminated after the average particle size of slurry in a reaction kettle reaches a preset particle size, so as to prepare the co-doped ternary cathode precursor, wherein the preset particle size is 3-16 micrometers.
8. The method according to any one of claims 4 to 6, wherein the precipitant is at least one of sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
9. The method for preparing the co-doped ternary cathode precursor according to any one of claims 4 to 6, wherein the reaction temperature of the co-precipitation chemical reaction is 25-65 ℃.
10. The ternary cathode material is characterized in that the general formula of the ternary cathode material is LiNixCoyMn1-x-yO2·aMgF2·bNd2O3And the cathode material is prepared from the codoped ternary cathode precursor of any one of claims 1 to 3 or the codoped ternary cathode precursor prepared by the method of any one of claims 4 to 9 and lithium, wherein the values of x, y, a and b satisfy the following conditions: x is more than 0 and less than 1, y is more than 0 and less than 1, a is more than 0.0003 and less than 0.02, and b is more than 0.0001 and less than 0.02.
11. A secondary battery comprising the ternary positive electrode material according to claim 10.
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