CN114477311A - Cobalt composite hydroxide, preparation method thereof, lithium ion battery positive electrode material and lithium ion battery - Google Patents
Cobalt composite hydroxide, preparation method thereof, lithium ion battery positive electrode material and lithium ion battery Download PDFInfo
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- CN114477311A CN114477311A CN202111610311.6A CN202111610311A CN114477311A CN 114477311 A CN114477311 A CN 114477311A CN 202111610311 A CN202111610311 A CN 202111610311A CN 114477311 A CN114477311 A CN 114477311A
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- composite hydroxide
- cobalt composite
- cobalt
- lithium ion
- ion battery
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 152
- 239000010941 cobalt Substances 0.000 title claims abstract description 152
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000002131 composite material Substances 0.000 title claims abstract description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 133
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims description 29
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 28
- 239000011164 primary particle Substances 0.000 claims description 23
- 239000008139 complexing agent Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 230000014759 maintenance of location Effects 0.000 abstract description 12
- 238000007086 side reaction Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000011572 manganese Substances 0.000 description 17
- 238000001878 scanning electron micrograph Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 150000004679 hydroxides Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 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
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 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
- 238000003801 milling Methods 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
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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Abstract
The invention relates to the field of lithium ion batteries, in particular to a cobalt composite hydroxide and a preparation method thereof, a lithium ion battery anode material and a lithium ion battery. The chemical formula of the cobalt composite hydroxide is NixCoyMnz(OH)2Wherein x + y + z is 1, x is less than or equal to 0.1, y is greater than or equal to 0.9, z is less than or equal to 0.1, and x and z are not 0 at the same time; the proportion of the 100 active crystal faces in the cobalt composite hydroxide is 10-40%. By doping Ni and/or Mn, the structural stability of the cobalt composite hydroxide can be effectively improved, and the specific capacity and the cycle of the battery are improvedThe ring capacity retention rate is reduced, and the cost is reduced; by exposing the active crystal face of 100 in a large area and covering the inactive face of 001, the rate capability of the anode material obtained after sintering can be improved, the contact area between the anode material and the electrolyte is reduced, the occurrence of side reaction of the anode material-electrolyte interface is reduced, and excellent cycle performance is obtained.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a cobalt composite hydroxide and a preparation method thereof, a lithium ion battery anode material and a lithium ion battery.
Background
Lithium cobaltate is an inorganic compound with the chemical formula LiCoO2It is generally used as a positive electrode material of a lithium ion battery, and the appearance of the positive electrode material is gray black powder. Some key indexes of the lithium ion battery, such as energy density, charge-discharge rate, safety and the like, are mainly limited by the anode material.
At present, lithium cobaltate cathode material is a relatively mature cathode material, and has the characteristics of high energy density and stable discharge voltage, so that the lithium cobaltate cathode material is widely applied to the field of 3C (short for three electronic products, namely computers, communication products and consumer electronics) digital products. However, the lithium cobaltate material has the defects of low specific capacity, poor safety, high cost and the like.
In addition, the cathode material may generate a battery-electrolyte interface side reaction during a long cycle, which may cause problems of cathode material dissolution, increased internal resistance of the battery, poor thermal safety, rapid charge-discharge cycle capacity decay, and the like.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a cobalt composite hydroxide, which can effectively improve the structural stability of the cobalt composite hydroxide, improve the specific capacity and the circulating capacity retention rate of a battery and reduce the cost by doping Ni and/or Mn; the proportion of each element in the cobalt composite hydroxide is in a specific range, the cobalt composite hydroxide with a 100 active surface exposed structure can be obtained, the proportion of a 100 active crystal face of the cobalt composite hydroxide is kept between 10% and 40%, the 100 active crystal face is exposed in a large area, and a 001 inactive face is covered, so that the rate performance of a positive electrode material obtained after sintering can be improved, the contact area between the positive electrode material and electrolyte is reduced, the occurrence of side reactions at the interface of the positive electrode material and the electrolyte is reduced, and excellent cycle performance is obtained.
The second purpose of the invention is to provide the preparation method of the cobalt composite hydroxide, which has the advantages of simple operation, mild conditions, suitability for mass production and the like.
The third purpose of the present invention is to provide a lithium ion battery positive electrode material which has excellent rate capability and excellent cycle performance because the contact area between the positive electrode material and the electrolyte is reduced and the occurrence of side reactions at the positive electrode material-electrolyte interface is reduced.
The fourth purpose of the invention is to provide a lithium ion battery which has the advantages of high energy density, excellent rate capability and cycle performance, high safety performance and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a cobalt composite hydroxide, wherein the chemical formula of the cobalt composite hydroxide is NixCoyMnz(OH)2Wherein x + y + z is 1, x is less than or equal to 0.1, y is greater than or equal to 0.9, z is less than or equal to 0.1, and x and z are not 0 at the same time;
the proportion of the 100 active crystal faces in the cobalt composite hydroxide is 10-40% (12%, 14%, 16%, 18%, 20%, 25%, 30%, 35% or 38% can be selected).
Wherein x can be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1; y can be selected from 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98 or 0.99; z may be selected from 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1.
According to the cobalt composite hydroxide provided by the invention, by doping Ni and/or Mn, the structural stability of the cobalt composite hydroxide can be effectively improved, the specific capacity and the circulating capacity retention rate of a battery are improved, and the cost is reduced.
In addition, the invention can obtain the cobalt composite hydroxide with a 100 active surface exposed structure by enabling the proportion of each element in the cobalt composite hydroxide to be in a specific range, and the proportion of a 100 active crystal face of the cobalt composite hydroxide is kept between 10 and 40 percent, and the 001 inactive face is covered by exposing the 100 active crystal face in a large area, so that the rate capability of the cathode material obtained after sintering can be improved, the contact area between the cathode material and the electrolyte is reduced, the occurrence of side reactions at the interface of the cathode material and the electrolyte is reduced, and the excellent cycle performance is obtained.
Specifically, the cobalt composite hydroxide is used as Li of a precursor of the cathode material on different crystal planes+The diffusion rate difference is large, and Li of the layered oxide anode precursor on a 100 crystal face+Diffusion is faster, and 001 crystal face Li+The transmission speed is slow. Therefore, the invention enables the active crystal face to be exposed in a large area by regulating the preferred orientation of the crystal face of the primary particle and the structure of the secondary particle, and improves the electrochemical performance of the cobalt composite hydroxide.
In addition, the positive electrode material obtained by lithium mixing and sintering the cobalt composite hydroxide provided by the invention can inherit the exposed structural characteristics of the active surface of the cobalt composite hydroxide 100.
Preferably, the primary particles of the cobalt composite hydroxide are in the shape of hexagonal prisms.
Preferably, the thickness of the cobalt composite hydroxide primary particles is 0.2-1.0 μm; including but not limited to any one of 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or a range of values therebetween.
Preferably, the length of the primary particles of the cobalt composite hydroxide is 1.0 to 2.5 μm, including but not limited to any one of 1.2 μm, 1.4 μm, 1.5 μm, 1.7 μm, 1.9 μm, 2.0 μm, 2.2 μm, 2.4 μm or a range between any two.
Preferably, the micro-morphology of the cobalt composite hydroxide provided by the invention is a three-dimensional flower-like structure which is formed by a single-layer sheet consisting of a plurality of crystal grains.
Wherein, the primary particles described in the present application mean a single-layer flake composed of a plurality of crystal grains, the flake is in the shape of a hexagonal prism and is a sheet structure with a hexagonal cross section; the secondary particles referred to in this application are particles having a three-dimensional flower-like structure.
The 100 active crystal face occupation ratio is related to the thickness and the length of the primary particles of the cobalt composite hydroxide, the higher the active face occupation ratio is, the more lithium ion diffusion channels are on the surface of the particles of the cathode material obtained after the cobalt composite hydroxide is sintered, and the better the rate capability of the material is.
The primary particles of the cobalt composite hydroxide adopt the thickness and length ranges, so that sufficient growth space can be provided for the primary particles, the 100 active surface occupation ratio of the cobalt composite hydroxide obtained in the range is high, and the rate capability and the cycle performance of the anode material prepared from the cobalt composite hydroxide are improved.
Preferably, the crystal grain size of the cobalt composite hydroxide along the 001 inactive crystal face direction is
Including but not limited to
A point value of any one of them, or a range value between any two.
The size of the crystal grains can affect the reactivity of the cobalt composite hydroxide and the lithium carbonate in the lithium mixing sintering process and the ratio table of the sintered positive electrode material, and further can affect the dispersion state of the material and the safety of the material. The adoption of the grain size in the range is beneficial to improving the dispersibility of the materials and avoiding the agglomeration of the materials, and the safety performance of the anode material obtained after sintering is good.
Preferably, the ratio of the grain size of the cobalt composite hydroxide along the 001 inactive crystal face direction to the grain size along the 100 active crystal face direction is 0.8-1.0, and 0.9 can be selected.
The size ratio of the crystal grains can reflect the active surface proportion in the crystal grains. The larger the ratio is, the higher the proportion of 100 active faces in the crystal grains is, and the higher the proportion of 100 active crystal faces in a single crystal grain is, the more excellent the rate performance of the material is. The size ratio in the range is favorable for improving the rate capability of the material.
Wherein, the schematic diagram of the grain sizes of the cobalt composite hydroxide along different directions is shown in figure 1.
The schematic structural view of the primary particles of the cobalt composite hydroxide is shown in fig. 2.
Preferably, the D50 particle size of the cobalt composite hydroxide is 9-11 μm; 10 μm was also selected.
Preferably, the ratio (D95-D5)/D50 of the difference between the D95 particle diameter and the D5 particle diameter of the cobalt composite hydroxide and the D50 particle diameter is 0.9-1.1; 0.95, 1.0 or 1.05 can also be selected.
The uniform granularity is beneficial to avoiding the melting agglomeration of the anode material prepared from the cobalt composite hydroxide in the sintering process, reducing the polarization phenomenon caused by the uneven granularity of the anode material in the battery charging and discharging process and improving the cycle performance of the battery.
The invention provides a preparation method of the cobalt composite hydroxide, which comprises the following steps:
adding a mixed metal salt solution, a precipitator solution and a complexing agent into a base solution under an inert atmosphere, carrying out coprecipitation reaction, and after precipitate particles grow to a target particle size, sequentially carrying out solid-liquid separation, sieving and demagnetizing to obtain the cobalt composite hydroxide;
wherein the metal element in the mixed metal salt solution comprises at least one of nickel element and manganese element, and cobalt element; and the molar ratio of the nickel element, the cobalt element and the manganese element is 0-10 (1, 2, 3, 4, 5, 6, 7, 8 or 9 can be selected): 90-100 (91, 92, 93, 94, 95, 96, 97, 98 or 99 can be selected): 0-10 (1, 2, 3, 4, 5, 6, 7, 8 or 9 can be selected).
The cobalt composite hydroxide with a specific ratio and a 100 active surface exposed structure can be obtained by adopting the preparation method.
In addition, the preparation method of the cobalt composite hydroxide provided by the invention has the advantages of simple operation, mild conditions, suitability for mass production and the like.
The mixed metal salt solution is a solution containing a nickel element and a cobalt element, or a solution containing a manganese element and a cobalt element, or a solution containing a nickel element, a cobalt element and a manganese element.
The mixed metal salt solution is prepared by dissolving metal elements in water, which is beneficial to improving the distribution uniformity of Ni, Co and Mn in the coprecipitation reaction process.
In addition, the coprecipitation reaction is carried out under the inert atmosphere, so that the materials in the reaction process can be prevented from being oxidized.
Preferably, the ratio of the feed flow rates of the mixed metal salt solution, the precipitant solution and the complexing agent is 1: 0.35-0.42 (0.36, 0.37, 0.38, 0.39, 0.40 or 0.41 can be selected): 0.012-0.175 (0.015, 0.02, 0.03, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.15, 0.16 or 0.17 can be selected).
By adjusting the feed flow ratio of the raw materials in the coprecipitation reaction process, a series of hydroxides with different primary particle thicknesses, lengths, secondary particle morphologies and grain sizes can be obtained.
Preferably, the molar concentration of metal ions in the mixed metal salt solution is 1-5 mol/L; including but not limited to, a point value of any one of 2mol/L, 3mol/L, 4mol/L, or a range value between any two.
Preferably, the mass fraction of the precipitant solution is 30-35%; including but not limited to, a point value of any one of 31%, 32%, 33%, 34%, or a range value between any two.
Preferably, the mass fraction of the complexing agent is 18% to 25%, including but not limited to any one of 19%, 20%, 21%, 22%, 23%, 24% or a range between any two.
The precipitant solution and the complexing agent with the above concentrations are adopted, which is helpful for reducing the reaction wastewater amount.
In addition, the concentration of metal ions in the mixed metal salt solution and the concentrations of the precipitant solution and the complexing agent also have certain influence on the physicochemical properties of the cobalt composite hydroxide, and the concentration within the range is favorable for improving the proportion of the 100 active crystal face in the cobalt composite hydroxide.
Preferably, the target particle size of the precipitate particles is 8-15 μm; it is also possible to select 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm.
Preferably, in the process of the coprecipitation reaction, the pH of the mixture is 10.5 to 12.5 (11, 11.5 or 12 may be selected), and the temperature of the mixture is 40 to 60 ℃ (45 ℃, 50 ℃ or 55 ℃ may be selected).
The preparation temperature and the pH value are adopted, so that the occupation ratio of the 100 active crystal face is improved.
In some specific embodiments of the invention, the nickel source used in the mixed metal salt solution comprises at least one of nickel chloride, nickel sulfate, and nickel nitrate;
preferably, the cobalt source used in the mixed metal salt solution comprises at least one of cobalt chloride, cobalt sulfate and cobalt nitrate;
preferably, the source of manganese used in the mixed metal salt solution comprises at least one of manganese chloride, manganese sulfate and manganese nitrate;
preferably, the gas used for the inert atmosphere comprises nitrogen and/or argon.
Preferably, after the solid-liquid separation, the method further comprises the step of washing and drying the separated solid material.
More preferably, the drying temperature is 100-150 ℃ (optionally 110 ℃, 120 ℃, 130 ℃ or 140 ℃), and the drying time is 10-15 h (optionally 11h, 12h, 13h or 14 h).
Preferably, the base solution consists essentially of a precipitant solution and a complexing agent.
Preferably, the precipitating agent comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the complexing agent comprises ammonia and/or EDTA (ethylenediaminetetraacetic acid).
The invention also provides a lithium ion battery anode material which is prepared by sintering the cobalt composite hydroxide or the cobalt composite hydroxide prepared by the preparation method of the cobalt composite hydroxide through lithium mixing.
The cathode material has excellent rate performance, and because the contact area between the cathode material and the electrolyte is reduced, the occurrence of cathode material-electrolyte interface side reaction is reduced, so that the cycle performance is excellent.
The invention also provides a lithium ion battery, which comprises the anode prepared from the lithium ion battery anode material.
The lithium ion battery has the advantages of high energy density, excellent rate capability and cycle performance, high safety performance and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the cobalt composite hydroxide provided by the invention, by doping Ni and/or Mn, the structural stability of the cobalt composite hydroxide can be effectively improved, the specific capacity and the circulating capacity retention rate of a battery are improved, and the cost is reduced.
(2) According to the cobalt composite hydroxide provided by the invention, the proportion of each element in the cobalt composite hydroxide is in a specific range, the hydroxide with a 100 active surface exposed structure can be obtained, the proportion of a 100 active crystal surface of the hydroxide is kept in a range of 10-40%, the 100 active crystal surface is exposed in a large area, and a 001 inactive surface is covered, so that the rate performance of a positive electrode material obtained after sintering can be improved, the contact area between the positive electrode material and an electrolyte is reduced, the occurrence of side reactions of the positive electrode material-electrolyte interface is reduced, and excellent cycle performance is obtained.
(3) The lithium ion battery anode material provided by the invention has the advantages of excellent rate capability, excellent cycle performance and high safety performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of the grain sizes of cobalt composite hydroxide provided by the present invention along different directions;
FIG. 2 is a schematic structural view of primary particles of a cobalt composite hydroxide provided by the present invention;
FIG. 3 is an SEM image of cobalt composite hydroxide provided in example 1 of the present invention at a magnification of 1000;
FIG. 4 is an SEM photograph of cobalt composite hydroxide with a magnification of 5000, which is provided in example 1 of the present invention;
FIG. 5 is an SEM image of cobalt composite hydroxide provided in example 2 of the present invention at a magnification of 1000;
FIG. 6 is an SEM photograph of cobalt composite hydroxide with a magnification of 5000, provided in example 2 of the present invention;
FIG. 7 is an SEM image of cobalt composite hydroxide provided in example 3 of the present invention at a magnification of 1000;
FIG. 8 is an SEM photograph of example 3 of the present invention showing that the cobalt composite hydroxide has a magnification of 5000;
FIG. 9 is an SEM photograph of a cobalt composite hydroxide provided in example 4 of the present invention at a magnification of 1000;
FIG. 10 is an SEM photograph of cobalt composite hydroxide with the magnification of 5000, provided in example 4 of the present invention;
FIG. 11 is an SEM image of comparative example 1 of the present invention, in which the magnification is 1000;
FIG. 12 is an SEM photograph of comparative example 1 of the present invention, in which the magnification is 5000;
FIG. 13 is an SEM image of comparative example 2 of the present invention, in which the magnification is 1000;
FIG. 14 is an SEM photograph of comparative example 2 of the present invention, in which the magnification is 5000;
FIG. 15 is an SEM photograph of comparative example 3 of the present invention, in which the magnification is 1000;
FIG. 16 is an SEM photograph of comparative example 3 of the present invention, in which the magnification is 5000;
figure 17 is an XRD pattern of cobalt composite hydroxide provided in example 1 of the present invention;
figure 18 is an XRD pattern of cobalt composite hydroxide provided in example 2 of the present invention;
figure 19 is an XRD pattern of cobalt composite hydroxide provided in example 3 of the present invention;
figure 20 is an XRD pattern of cobalt composite hydroxide provided in example 4 of the present invention;
fig. 21 is an XRD pattern of cobalt composite hydroxide provided in comparative example 1 of the present invention;
FIG. 22 is an XRD pattern of a cobalt composite hydroxide provided in comparative example 2 of the present invention;
fig. 23 is an XRD pattern of the cobalt composite hydroxide provided in comparative example 3 of the present invention;
FIG. 24 is a CP diagram (a) of a cobalt composite hydroxide provided in example 1 of the present invention and EDS energy spectra of a nickel element (b), a cobalt element (c) and a manganese element (d);
FIG. 25 is an SEM image of 1000 magnification of a positive electrode material made of cobalt composite hydroxide of example 1 according to the present invention;
FIG. 26 is an SEM image of a positive electrode material prepared from the cobalt composite hydroxide of example 1 at a magnification of 5000 in accordance with the present invention;
FIG. 27 is an SEM image of 1000 magnification of a positive electrode material made of cobalt composite hydroxide of example 2 according to the present invention;
fig. 28 is an SEM image of a positive electrode material prepared from the cobalt composite hydroxide of example 2 according to the present invention at a magnification of 5000;
fig. 29 is an SEM image of a positive electrode material prepared from comparative example 1 cobalt composite hydroxide according to the present invention at a magnification of 1000;
fig. 30 is an SEM image of 5000 magnification of a positive electrode material prepared from comparative example 1 cobalt composite hydroxide according to the present invention;
fig. 31 is an SEM image of a positive electrode material prepared from comparative example 2 cobalt composite hydroxide according to the present invention at a magnification of 1000;
fig. 32 is an SEM image of a positive electrode material prepared from comparative example 2 cobalt composite hydroxide according to the present invention at a magnification of 5000.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are a part of the embodiments of the present invention, rather than all of the embodiments, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
FIG. 1 is a schematic view of the grain sizes of cobalt composite hydroxides provided by the present invention along different directions; fig. 2 is a schematic structural view of primary particles of the cobalt composite hydroxide provided by the present invention.
Example 1
Cobalt composite hydroxide Ni provided in this example0.05Co0.9Mn0.05(OH)2The preparation method comprises the following steps (the reaction process is carried out under a nitrogen atmosphere):
(1) dissolving nickel chloride, cobalt chloride and manganese chloride in water, and uniformly mixing to obtain a mixed metal salt solution; wherein, the molar ratio of nickel, cobalt and manganese elements is 5: 90: 5, the molar concentration of metal ions in the mixed metal salt solution is 2 mol/L;
preparing a sodium hydroxide solution with the mass fraction of 32% as a precipitator solution, and preparing ammonia water with the mass fraction of 21% as a complexing agent; mixing the 32% sodium hydroxide solution with 21% ammonia water by mass percent, and adding water to prepare a base solution with the pH value of 11.5 and the ammonia concentration of 8.0 g/L;
(2) adding the mixed metal salt solution, the precipitant solution and the complexing agent obtained in the step (1) into a base solution in a nitrogen atmosphere with the purity of more than or equal to 99.9% by selecting a reaction kettle with the volume of 100L for coprecipitation reaction; wherein the feeding flow ratio of the mixed metal salt solution, the precipitant solution and the complexing agent is 1: 0.4: 0.04; continuously stirring in the reaction process, and controlling the pH of the mixed material to be 11.2 and the temperature of the mixed material to be 50 ℃ in the reaction process;
(3) stopping feeding when precipitate particles in the reaction kettle grow to the particle size of 10 mu m, filtering the mixed material, and sequentially performing alkali washing, water washing, drying (drying at 120 ℃ for 12h), sieving and demagnetizing on the solid material obtained after filtering to obtain the cobalt composite hydroxide Ni0.05Co0.9Mn0.05(OH)2。
Example 2
This example provides a cobalt composite hydroxide Ni0.05Co0.9Mn0.05(OH)2The preparation method of (a) is substantially the same as in example 1 except that, in step (2), the feed flow ratio of the mixed metal salt solution, the precipitant solution, and the complexing agent is replaced with 1: 0.4: 0.06.
example 3
This example provides a cobalt composite hydroxide Ni0.1Co0.9(OH)2The preparation method comprises the following steps (the reaction process is carried out under the nitrogen atmosphere):
(1) dissolving nickel sulfate and cobalt sulfate in water, and uniformly mixing to obtain a mixed metal salt solution; wherein the molar ratio of the nickel element to the cobalt element is 10: 90, the molar concentration of the metal ions in the mixed metal salt solution is 2 mol/L;
preparing a sodium hydroxide solution with the mass fraction of 32% as a precipitator solution, and preparing ammonia water with the mass fraction of 21% as a complexing agent; mixing the 32% sodium hydroxide solution with 21% ammonia water by mass percent, and adding water to prepare a base solution with the pH value of 11.5 and the ammonia concentration of 8.0 g/L;
(2) exactly the same as the step (2) of example 1;
(3) exactly the same as in step (3) of example 1.
Example 4
The cobalt complex provided by the embodimentSynthetic hydroxide Co0.9Mn0.1(OH)2The preparation method comprises the following steps (the reaction process is carried out under a nitrogen atmosphere):
(1) dissolving cobalt nitrate and manganese nitrate in water, and uniformly mixing to obtain a mixed metal salt solution; wherein the molar ratio of the manganese element to the cobalt element is 10: 90, the molar concentration of the metal ions in the mixed metal salt solution is 2 mol/L;
preparing a sodium hydroxide solution with the mass fraction of 32% as a precipitator solution, and preparing ammonia water with the mass fraction of 21% as a complexing agent; mixing the 32% sodium hydroxide solution with 21% ammonia water by mass percent, and adding water to prepare a base solution with the pH value of 11.5 and the ammonia concentration of 8.0 g/L;
(2) exactly the same as the step (2) of example 1;
(3) exactly the same as in step (3) of example 1.
Example 5
This example provides a cobalt composite hydroxide Ni0.05Co0.9Mn0.05(OH)2The preparation method of (a) is substantially the same as that of example 1 except that: firstly, in the step (1), the molar concentration of metal ions in the mixed metal salt solution is 3mol/L, the mass fraction of the sodium hydroxide solution is 35%, and the mass fraction of ammonia water is 25%;
secondly, in the step (2), the feeding flow ratio of the mixed metal salt solution, the precipitant solution and the complexing agent is replaced by 1: 0.35: 0.17, and controlling the pH of the mixed material to be 11 and the temperature of the mixed material to be 40 ℃ in the reaction process.
Comparative example 1
Cobalt composite hydroxide Ni provided by this comparative example0.05Co0.9Mn0.05(OH)2The preparation method of (a) is substantially the same as in example 1 except that, in step (2), the feed flow ratio of the mixed metal salt solution, the precipitant solution, and the complexing agent is replaced with 1: 0.2: 0.2.
comparative example 2
Cobalt composite hydroxide Ni provided by this comparative example0.05Co0.9Mn0.05(OH)2The preparation method of (a) is substantially the same as in example 1 except that, in step (2), the feed flow ratio of the mixed metal salt solution, the precipitant solution, and the complexing agent is replaced with 1: 0.4: 0.02.
comparative example 3
Cobalt composite hydroxide Ni provided by this comparative example0.05Co0.9Mn0.05(OH)2The preparation method of (a) was substantially the same as in example 1 except that no nitrogen blanket was applied during the reaction to prepare a cobalt composite hydroxide.
Comparative example 4
Cobalt composite hydroxide Ni provided by this comparative example0.1Co0.8Mn0.1(OH)2The preparation method of (2) is basically the same as that of example 1, except that in the step (1), the molar ratio of nickel, cobalt and manganese elements in the mixed metal salt solution is 1: 8: 1.
experimental example 1
The thickness, length, 100 active crystal face ratio of the primary particles of the cobalt composite hydroxide obtained in each of the above examples and comparative examples, and the particle size of the cobalt composite hydroxide were measured, and the results are shown in table 1.
XRD detection was performed on the cobalt composite hydroxide prepared in each of the above examples and comparative examples, and the results are shown in table 2 below.
TABLE 1 physicochemical indexes of cobalt composite hydroxides of each group
TABLE 2 XRD diffraction phase data for cobalt composite hydroxides of each group
Scanning electron microscope tests (SEM) were performed on the cobalt composite hydroxides prepared in example 1, example 2, example 3, example 4, comparative example 1, comparative example 2, and comparative example 3, respectively, and the results were as shown in fig. 3 (example 1 at 1000-fold magnification) and fig. 4 (example 1 at 5000-fold magnification), fig. 5 (example 2 at 1000-fold magnification) and fig. 6 (example 2 at 5000-fold magnification), fig. 7 (example 3 at 1000-fold magnification) and fig. 8 (example 3 at 5000-fold magnification), fig. 9 (example 4 at 1000-fold magnification) and fig. 10 (example 4 at 5000-fold), fig. 11 (comparative example 1 at 1000-fold) and fig. 12 (comparative example 1 at 5000-fold), fig. 13 (comparative example 2 at 1000-fold) and fig. 14 (comparative example 2 at 5000-fold), fig. 15 (comparative example 3 at 1000-fold), and fig. 16 (comparative example 3 at 5000-fold), respectively.
And XRD detection was performed on the cobalt composite hydroxides prepared in example 1, example 2, example 3, example 4, comparative example 1, comparative example 2, and comparative example 3, and the results were shown in fig. 17, fig. 18, fig. 19, fig. 20, fig. 21, fig. 22, and fig. 23, respectively.
The cobalt composite hydroxide obtained in example 1 was subjected to CP (ion beam profile milling) cutting and EDS energy spectrum analysis, and the results are shown in fig. 24, in which fig. 24(a) is a cross-sectional view of cobalt composite hydroxide particles after CP cutting, fig. 24(b) is an EDS energy spectrum of a nickel element, fig. 24(c) is an EDS energy spectrum of a cobalt element, and fig. 24(d) is an EDS energy spectrum of a manganese element. As can be seen from fig. 24, the Ni, Co, and Mn elements in the cobalt composite hydroxide prepared in example 1 were uniformly distributed.
In addition, according to the present invention, TEM (transmission electron microscope) tests were performed on the cobalt composite hydroxide prepared in example 1, and it was found that the interplanar spacings of the surfaces of the primary particles of the cobalt composite hydroxide were respectively set to
In accordance with the interplanar spacing data obtained from the (001) plane and the (100) plane XRD diffraction results, respectively, it was confirmed that the exposed surfaces of the primary particles of cobalt composite hydroxide were the (001) plane and the (100) plane. The shape of the primary particles of the cobalt composite hydroxide was regular hexagonal nanoplate-like (refer to fig. 2), and the exposed active surface occupation ratio of the particle surface was calculated to be about 35% from the average thickness and length of the primary particles.
As can be seen from the SEM image of the cobalt composite hydroxide prepared in example 1, there was no agglomeration between particles.
Experimental example 2
The cobalt composite hydroxides obtained in the above examples and comparative examples were respectively subjected to lithium mixing and sintering to obtain groups of positive electrode materials, and then the particle sizes of the groups of positive electrode materials were measured and assembled into a lithium ion battery, and electrochemical performance tests were performed on the lithium ion battery, and the results are shown in table 3.
Table 3 particle size and electrochemical performance test results of each group of positive electrode materials
And Scanning Electron Microscope (SEM) tests were performed on the positive electrode materials obtained from the cobalt composite hydroxides obtained in example 1, example 2, comparative example 1 and comparative example 2, and the results are shown in fig. 25 (example 1 at 1000-fold magnification) and fig. 26 (example 1 at 5000-fold magnification), fig. 27 (example 2 at 1000-fold magnification) and fig. 28 (example 2 at 5000-fold magnification), fig. 29 (comparative example 1 at 1000-fold magnification) and fig. 30 (comparative example 1 at 5000-fold magnification), fig. 31 (comparative example 2 at 1000-fold) and fig. 32 (comparative example 2 at 5000-fold magnification), respectively.
As can be seen from fig. 25 and 26, the positive electrode material after sintering of the cobalt composite hydroxide in example 1 can inherit the structural morphology of the cobalt composite hydroxide, and the secondary particles are denser, and the gaps between the primary particles are filled up. In the electrical property test, 1C cycle test shows that the capacity retention rate of 100 circles is 94%; 5C cycle test shows that the capacity retention rate of 100 circles reaches 73%, and the rate performance and the cycle performance of the cathode material in the embodiment 1 are superior to those of each comparative example.
According to the SEM topography of example 3, example 4 and example 5, it can be seen that when the chemical formula of the cobalt composite hydroxide is NixCoyMnz(OH)2Wherein x + y + z is 1, x is less than or equal to 0.1, y is greater than or equal to 0.9, and z is less than or equal to 0.1, and the cobalt composite hydroxide with the similar secondary particle active surface exposed structure can be obtained by adjusting the element proportion in the range. And in subsequent electrical property tests of the anode material, the anode material shows excellent capacity and rate performance.
From comparisonThe data of example 1 show that the active surface proportion of the precursor prepared in comparative example 1 is increased to 57%, and the grain size reaches
After the cobalt composite hydroxide lithium mixed is sintered into the anode material, the melting agglomeration phenomenon occurs to material particles, the particle size distribution is widened, and the structure of the cobalt composite hydroxide with 100 active crystal faces exposed is damaged. In the electrical property test, 1C cycle test shows that the capacity retention rate of 100 circles is 85%; the capacity retention rate of 100 circles is reduced to 55 percent by 5C cycle test.
As can be seen from the data of comparative example 2, the particle size distribution of the precursor prepared in comparative example 2 was broadened after the feed flow rate of the complexing agent was reduced, and it was apparent that the particle size was not uniform in the cobalt composite hydroxide SEM. The primary particle thickness of the cobalt composite hydroxide prepared in comparative example 2 was about 0.1 μm, and the active surface proportion was 6%. A small amount of agglomeration occurs in the positive electrode material obtained after lithium mixing and sintering, and a large amount of gaps exist among primary particles. In the electrical property test, 1C cycle test shows that the capacity retention rate of 100 circles is 83%; 5C cycle test shows that the capacity retention rate of 100 cycles is 48%, and compared with the capacity retention rate of the battery in example 1, the capacity retention rate of the battery under high-rate discharge is obviously reduced.
As can be seen from the respective sets of data of comparative example 3, the secondary particle surface of the cobalt composite hydroxide prepared in comparative example 3 was in a disordered state, and had no structure in which the active surface was exposed. And XRD diffraction shows that the material is in an oxide state and has poor crystallinity, the particle size distribution (D95-D5)/D50 of the cobalt composite hydroxide reaches 2.66, and the particle size distribution is not uniform. In subsequent electrical property tests, both the material capacity and rate performance were inferior to example 1.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (10)
1. Cobalt composite hydroxide characterized in that the cobalt composite hydroxide has the chemical formula of NixCoyMnz(OH)2Wherein x + y + z is 1, x is less than or equal to 0.1, y is greater than or equal to 0.9, z is less than or equal to 0.1, and x and z are not 0 at the same time;
the proportion of the 100 active crystal faces in the cobalt composite hydroxide is 10-40%.
2. The cobalt composite hydroxide according to claim 1, wherein the primary particles of the cobalt composite hydroxide have a hexagonal prism shape;
preferably, the thickness of the cobalt composite hydroxide primary particles is 0.2-1.0 μm;
preferably, the length of the primary particles of the cobalt composite hydroxide is 1.0 to 2.5 μm.
3. The cobalt composite hydroxide according to claim 1, wherein the cobalt composite hydroxide has a crystal grain size in a 001 inactive crystal plane direction of
Preferably, the ratio of the grain size of the cobalt composite hydroxide along the 001 inactive crystal plane direction to the grain size along the 100 active crystal plane is 0.8 to 1.0.
4. The cobalt composite hydroxide according to claim 1, wherein the cobalt composite hydroxide has a D50 particle size of 9 to 11 μm;
preferably, the ratio (D95-D5)/D50 of the difference between the D95 particle diameter and the D5 particle diameter and the D50 particle diameter of the cobalt composite hydroxide is 0.9 to 1.1.
5. The method for producing a cobalt composite hydroxide according to any one of claims 1 to 4, characterized by comprising the steps of:
adding a mixed metal salt solution, a precipitator solution and a complexing agent into a base solution under an inert atmosphere, carrying out coprecipitation reaction, and after precipitate particles grow to a target particle size, sequentially carrying out solid-liquid separation, sieving and demagnetizing to obtain the cobalt composite hydroxide;
wherein the metal element in the mixed metal salt solution comprises at least one of nickel element and manganese element, and cobalt element; and the molar ratio of the nickel element, the cobalt element and the manganese element is 0-10: 90-100: 0 to 10.
6. The method of claim 5, wherein the ratio of the feed flow rates of the mixed metal salt solution, the precipitant solution, and the complexing agent is 1: 0.35-0.42: 0.012 to 0.175.
7. The preparation method according to claim 5, wherein the molar concentration of the metal ions in the mixed metal salt solution is 1-5 mol/L;
preferably, the mass fraction of the precipitant solution is 30-35%;
preferably, the mass fraction of the complexing agent is 18-25%.
8. The method according to claim 5, wherein the precipitate particles have a target particle size of 8 to 15 μm;
preferably, in the coprecipitation reaction process, the pH of the mixed material is 10.5-12.5, and the temperature of the mixed material is 40-60 ℃.
9. The lithium ion battery positive electrode material is prepared by sintering the cobalt composite hydroxide according to any one of claims 1 to 4 or the cobalt composite hydroxide prepared by the preparation method of the cobalt composite hydroxide according to any one of claims 5 to 8 through lithium mixing.
10. A lithium ion battery comprising a positive electrode prepared from the positive electrode material of claim 9.
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