CN114094095A - Spinel type positive electrode material, preparation method thereof and lithium ion battery positive electrode plate - Google Patents
Spinel type positive electrode material, preparation method thereof and lithium ion battery positive electrode plate Download PDFInfo
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- CN114094095A CN114094095A CN202111320834.7A CN202111320834A CN114094095A CN 114094095 A CN114094095 A CN 114094095A CN 202111320834 A CN202111320834 A CN 202111320834A CN 114094095 A CN114094095 A CN 114094095A
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 100
- 239000011029 spinel Substances 0.000 title claims abstract description 100
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 title claims description 50
- 238000002360 preparation method Methods 0.000 title description 32
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 37
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000010405 anode material Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 229910018162 SeO2 Inorganic materials 0.000 claims abstract description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 8
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 6
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 34
- 239000011572 manganese Substances 0.000 claims description 33
- 238000005245 sintering Methods 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 24
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 23
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 19
- 229910052797 bismuth Inorganic materials 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 238000005056 compaction Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 150000001242 acetic acid derivatives Chemical class 0.000 description 19
- 235000021317 phosphate Nutrition 0.000 description 19
- 229910013716 LiNi Inorganic materials 0.000 description 15
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 13
- 150000002823 nitrates Chemical class 0.000 description 12
- 150000004679 hydroxides Chemical class 0.000 description 11
- 229910052787 antimony Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 7
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 7
- 229910001947 lithium oxide Inorganic materials 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical class [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical class [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
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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
- H01M4/52—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a spinel type anode material, which comprises a coating oxide MOxThe lithium nickel manganese oxide of (1), wherein the oxide MOxThe mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01-1) to (99.99-99); said oxide MOxComprising B2O3、V2O5、SeO2、Sb2O3、Bi2O3Or SnO2Any one or a combination of at least two of them. In the spinel type anode material provided by the invention, the easily-melted coating precursor is coated, so that the lubricity of the surface of the material is increased, the sliding resistance among anode material particles is reduced, and the compaction density of the prepared anode plate is increased, thereby improving the energy density of a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a spinel type positive electrode material, and particularly relates to a spinel type positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate.
Background
The spinel type lithium nickel manganese oxide has higher reaction potential (more than 4.6V) and higher theoretical specific capacity (more than 140mAh/g), so the spinel type lithium nickel manganese oxide is prepared by the methodThe method is applied to a power battery system with high energy density. However, the spinel-type lithium nickel manganese oxide sintered at present has a regular octahedral structure, the sphericity is insufficient, and the lubricity among particles is poor. Therefore, the pole piece compaction of the material is low (less than 3.1 g/cm)3). Although increasing the particle size may promote bulk compaction to 3.2g/cm3On the other hand, the problem of kinetic reduction is brought about, large particles have large internal stress in the sintering process, and the particles are more easily broken in the pressing process.
How to reduce the sliding resistance among particles and improve the compacted density of the prepared electrode plate on the premise of not increasing the particle size is a technical problem to be solved urgently by the lithium ion battery cathode material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a spinel type positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a spinel type positive electrode material comprising a coating oxide MOxThe lithium nickel manganese oxide of (1), wherein the oxide MOxThe mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01-1) to (99.99-99). Said oxide MOxComprising B2O3、V2O5、SeO2、Sb2O3、Bi2O3Or SnO2Any one or a combination of at least two of them.
Said oxide MOxThe mass ratio of lithium nickel manganese oxide to lithium nickel manganese oxide is (0.01 to 1): (99.99 to 99), and may be, for example, 0.01:99.99, 0.1:99.9, 0.2:99.8, 0.5:99.5 or 1:99, but is not limited to the values recited, and other values not recited in the numerical range are also applicable.
Said oxide MOxIncludedB2O3、V2O5、SeO2、Sb2O3、Bi2O3Or SnO2Any one or a combination of at least two of them. A typical but non-limiting combination includes B2O3And V2O5Combination of (1), V2O5And SeO2Combination of (5), SeO2And Sb2O3Combination of (A) and (B)2O3And Bi2O3Combination of (A) and (B)2O3And SnO2Combination of (A) and (B)2O3、V2O5And SeO2Combination of (5), SeO2、Sb2O3、Bi2O3And SnO2Or a combination of (A) and (B), or V2O5、SeO2、Sb2O3And Bi2O3Combinations of (a) and (b).
According to the spinel type cathode material provided by the invention, the spinel lithium nickel manganese oxide cathode material is coated by the oxide, so that the lubricity of the surface of the material is increased, the compaction density of a cathode plate is improved on the premise of not increasing the size of the material, and the energy density of a lithium ion battery is improved.
The oxide MO provided by the inventionxDue to the resulting oxide MO in the coating processxThe melting point of the coating precursor is low, for example, the melting point of the coating precursor of B is only about 200 ℃, while the coating substance provided by the invention has Bi with the highest melting point, the melting point of the coating precursor is about 400 ℃, and in the sintering process, the oxide MOxCan be dispersed in a molten form and uniformly attached to the surface of the lithium nickel manganese oxide, so that the lubricity of the surface of the material is improved, and the energy density is improved.
Preferably, the chemical formula of the lithium nickel manganese oxide is LiNiyMn2-yO4Wherein y is 0.2-0.8, preferably LiNi0.5Mn1.5O4. For example, it may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8, but is not limited to the values recited, and other values not recited within the range of values are also applicable.
Preferably, the coating comprises a face coating.
Preferably, the spinel type positive electrode material includes a secondary sphere morphology and/or a single crystal morphology.
Preferably, when the spinel type positive electrode material is in a secondary sphere form, the particle diameter D is50Is 18 μm to 35 μm, and may be, for example, 18 μm, 20 μm, 25 μm, 30 μm or 35 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
When the spinel type anode material is in a single crystal form, the particle diameter D50From 5 μm to 16 μm, and may be, for example, 5 μm, 8 μm, 10 μm, 15 μm or 16 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In a second aspect, the present invention provides a method for preparing the spinel type cathode material according to the first aspect, the method comprising:
mixing a lithium source, a nickel source, a manganese source and a coating precursor to obtain a mixture; and
and sintering the mixture to obtain the spinel type cathode material.
The spinel type anode material provided by the invention can be prepared by mixing the coating precursor with a lithium source, a nickel source and a manganese source and carrying out one-step co-sintering.
Preferably, the lithium source comprises any one or a combination of at least two of lithium oxide, hydroxide, nitrate, acetate or phosphate, typical but non-limiting combinations include lithium oxide and hydroxide combinations, lithium nitrate and acetate combinations, lithium acetate and phosphate combinations, lithium hydroxide and nitrate combinations, lithium nitrate and acetate combinations, lithium oxide, hydroxide and nitrate combinations, lithium oxide, acetate and phosphate combinations, lithium nitrate, acetate and phosphate combinations, lithium oxide, hydroxide, nitrate, acetate and acetate combinations, lithium hydroxide, nitrate, acetate and phosphate combinations, or lithium oxide, hydroxide, nitrate, acetate and phosphate combinations.
Preferably, the nickel source comprises any one of, or a combination of at least two of, nickel oxides, hydroxides, nitrates, acetates or phosphates, typical but non-limiting combinations include nickel oxides and hydroxides, nickel nitrates and acetates, nickel acetates and phosphates, nickel hydroxides and nitrates, nickel nitrates and acetates, nickel oxides, hydroxides and nitrates, nickel oxides, acetates and phosphates, nickel nitrates, acetates and phosphates, nickel oxides, hydroxides, nitrates, acetates and acetates, nickel hydroxides, nitrates, acetates and phosphates, or nickel oxides, hydroxides, nitrates, acetates and phosphates.
Preferably, the manganese source comprises any one or a combination of at least two of manganese oxides, hydroxides, nitrates, acetates or phosphates, typical but non-limiting combinations include combinations of manganese oxides and hydroxides, manganese nitrates and acetates, manganese acetates and phosphates, manganese hydroxides and nitrates, manganese nitrates and acetates, manganese oxides, hydroxides and nitrates, manganese oxides, acetates and phosphates, manganese nitrates, acetates and phosphates, manganese oxides, hydroxides, nitrates, acetates and acetates, manganese hydroxides, acetates, phosphates, or manganese oxides, hydroxides, nitrates, acetates and phosphates, or combinations of manganese oxides, hydroxides, nitrates, acetates and phosphates.
Preferably, the coating precursor comprises any one or a combination of at least two of M hydroxide, oxide or acetate, typical but non-limiting combinations include M hydroxide in combination with M oxide, M oxide in combination with M acetate, M hydroxide in combination with M acetate, or M hydroxide, M oxide in combination with M acetate. The M includes any one or a combination of at least two of B, V, Se, Sb, Bi, or Sn, and typical but non-limiting combinations include B in combination with V, V in combination with Se, Se in combination with Sb, Sb in combination with Bi, Bi in combination with Sn, B, V in combination with Se, V, Se in combination with Sb, Se, Sb in combination with Bi, Sb, Bi in combination with Sn, B, V, Se in combination with Sb, V, Se, Sb in combination with Bi, or V, Se, Sb, Bi in combination with Sn.
The oxide of M comprises an oxide of M and/or a hydrate of the oxide.
Preferably, the sintering temperature is from 400 ℃ to 550 ℃, for example, 400 ℃, 450 ℃, 500 ℃, 525 ℃ or 550 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the sintering time is 12h to 32h, for example 12h, 18h, 20h, 25h, 30h or 32h, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a third aspect, the present invention provides a method for preparing the spinel type cathode material according to the first aspect, the method comprising:
mixing the lithium nickel manganese oxide with the coating precursor to obtain a mixture; and
and sintering the mixture to obtain the spinel type cathode material.
The spinel type cathode material provided by the invention can also be prepared by mixing a coating precursor and a finished product of spinel type lithium nickel manganese oxide material and then sintering.
Preferably, the coating precursor comprises any one or a combination of at least two of M hydroxide, oxide hydrate or acetate, and typical but non-limiting combinations include M hydroxide in combination with M oxide, M oxide hydrate in combination with M acetate, M hydroxide in combination with M acetate, or M hydroxide, M oxide hydrate in combination with M acetate. The M includes any one or a combination of at least two of B, V, Se, Sb, Bi, or Sn, and typical but non-limiting combinations include B in combination with V, V in combination with Se, Se in combination with Sb, Sb in combination with Bi, Bi in combination with Sn, B, V in combination with Se, V, Se in combination with Sb, Se, Sb in combination with Bi, Sb, Bi in combination with Sn, B, V, Se in combination with Sb, V, Se, Sb in combination with Bi, or V, Se, Sb, Bi in combination with Sn.
The oxide of M comprises an oxide of M and/or a hydrate of the oxide.
Preferably, the sintering temperature is 150 ℃ to 350 ℃, for example 150 ℃, 200 ℃, 250 ℃, 300 ℃ or 350 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the sintering time is 6h to 24h, for example 6h, 10h, 12h, 15h, 18h, 20h or 24h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
In a fourth aspect, the invention provides a lithium ion battery positive plate, which contains the spinel type positive electrode material according to the first aspect.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the spinel type anode material provided by the invention is coated with the easily-melted coating precursor, so that the lubricity of the surface of the material is increased, the sliding resistance among anode material particles is reduced, and the compaction density of the prepared anode plate is increased, thereby improving the energy density of a lithium ion battery.
(2) The invention provides two preparation methods of spinel type anode materials, effectively realizes coating of oxide with easily-meltable precursor, improves the lubricity of the surface of the material, and has excellent electrochemical performance, simple preparation process and high production efficiency.
Detailed Description
According to the spinel lithium nickel manganese oxide positive electrode material provided in the prior art, a technical scheme is that airflow is adopted to crush and grade lithium nickel manganese oxide gathered together, and through controlling the relation between secondary calcination temperature and time, lithium nickel manganese oxide single crystals grow at high temperature according to conditions, air is introduced in a cooling stage, single crystal granular lithium nickel manganese oxide is prepared, and the compaction density and the tap density of a positive electrode plate are improved. According to another technical scheme, polytetrafluoroethylene is used as the binder, so that the volume expansion of the pole piece can be inhibited on the premise of ensuring the rigid structure of the pole piece, a solvent is not added for preparing the slurry, the process flow is simplified, and the compaction density is improved. The positive electrode material obtained by the method can improve the overall compaction density, but can bring the problem of reduced dynamics, and the material has larger internal stress in the sintering process and is more easily broken in the pressing process.
In order to solve the technical problems, the spinel type anode material provided by the invention is coated with the easily-melted coating precursor, so that the lubricity of the surface of the material is increased, the sliding resistance among anode material particles is reduced, and the compaction density of the prepared anode plate is increased, thereby improving the energy density of a lithium ion battery.
The present invention will be described in further detail with reference to the following embodiments. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a secondary sphere shape D50The particle size was 25 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And Sn (CH)3COO)4Obtaining a mixture; sintering the mixture for 24 hours at the temperature of 500 ℃ to obtain the productTo the spinel type positive electrode material.
Example 2
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.01: 99.9; the spinel type anode material is in a secondary sphere shape D50The particle size was 18 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixed Ni (OH)2、Mn(OH)4LiOH and Sn (CH)3COO)4Obtaining a mixture; and sintering the obtained mixture for 32 hours at the temperature of 400 ℃ to obtain the spinel type cathode material.
Example 3
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 1: 99; the spinel type anode material is in a secondary sphere shape D50The particle size was 35 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixed NiO, MnO2、Li2O and Sn (CH)3COO)4Obtaining a mixture; and sintering the obtained mixture for 12 hours at the temperature of 550 ℃ to obtain the spinel type cathode material.
Example 4
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a secondary sphere shape D50The particle size was 25 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3With SnO2·H2O, obtaining a mixture; and sintering the obtained mixture for 24 hours at the temperature of 500 ℃ to obtain the spinel type cathode material.
Example 5
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a secondary sphere shape D50The particle size was 25 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And Sn (OH)4Obtaining a mixture; and sintering the obtained mixture for 24 hours at the temperature of 500 ℃ to obtain the spinel type cathode material.
Example 6
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a secondary sphere shape D50The particle size was 25 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixed LiNi0.5Mn1.5O4And Sn (CH)3COO)4Obtaining a mixture; and sintering the obtained mixture for 12h at the temperature of 200 ℃ to obtain the spinel type cathode material.
Example 7
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.01: 99.99; the spinel type anode material is in a secondary sphere shape D50The particle size was 18 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixed LiNi0.5Mn1.5O4And Sn (CH)3COO)4Obtaining a mixture; and sintering the obtained mixture for 24 hours at the temperature of 150 ℃ to obtain the spinel type cathode material.
Example 8
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 1: 99; the spinel type anode material is in a secondary sphere shape D50The particle size was 18 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixed LiNi0.5Mn1.5O4And Sn (CH)3COO)4Obtaining a mixture; and sintering the obtained mixture for 12 hours at the temperature of 350 ℃ to obtain the spinel type cathode material.
Example 9
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a secondary sphere shape D50The particle size was 25 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixed LiNi0.5Mn1.5O4With SnO2·H2O, obtaining a mixture; and sintering the obtained mixture for 12h at the temperature of 200 ℃ to obtain the spinel type cathode material.
Example 10
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinelThe positive electrode material is in the form of secondary spheres D50The particle size was 25 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixed LiNi0.5Mn1.5O4And Sn (OH)4Obtaining a mixture; and sintering the obtained mixture for 12h at the temperature of 200 ℃ to obtain the spinel type cathode material.
Example 11
This example provides a spinel-type cathode material, except that the chemical formula of lithium nickel manganese oxide is LiNi0.2Mn1.8O4Except that, the remaining components and the preparation method were the same as in example 1.
Example 12
This example provides a spinel-type cathode material, except that the chemical formula of lithium nickel manganese oxide is LiNi0.8Mn1.2O4Except that, the remaining components and the preparation method were the same as in example 1.
Example 13
This example provides a spinel-type cathode material, except that the chemical formula of lithium nickel manganese oxide is LiNi0.2Mn1.8O4Except that, the remaining components and the preparation method were the same as in example 6.
Example 14
This example provides a spinel-type cathode material, except that the chemical formula of lithium nickel manganese oxide is LiNi0.8Mn1.2O4Except that, the remaining components and the preparation method were the same as in example 6.
Example 15
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a single crystal form, D50The particle size was 12 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And Sn(CH3COO)4Obtaining a mixture; and sintering the obtained mixture for 24 hours at the temperature of 500 ℃, and crushing to obtain the spinel type cathode material.
Example 16
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a single crystal form, D50The particle size was 5 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And Sn (CH)3COO)4Obtaining a mixture; and sintering the obtained mixture for 18h at the temperature of 450 ℃, and crushing to obtain the spinel type cathode material.
Example 17
This example provides a spinel type positive electrode material comprising coated SnO2LiNi of (2)0.5Mn1.5O4，SnO2And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a single crystal form, D50The particle size was 16 μm.
The preparation method of the spinel type cathode material comprises the following steps: mixing of Ni (NO)3)2、Mn(NO3)4、LiNO3And Sn (CH)3COO)4Obtaining a mixture; and sintering the obtained mixture for 32h at the temperature of 550 ℃, and crushing to obtain the spinel type cathode material.
Example 18
This example provides a spinel type cathode material, except for coating B2O3The coating precursor is B (CH)3COO)3Except that the other components and the preparation method are the same as those of the example 1.
Example 19
This example provides a spinel type cathode material, except for coating V2O5The coating precursor is V (CH)3COO)5Except that the other components and the preparation method are the same as those of the example 1.
Example 20
This example provides a spinel type positive electrode material, except for coated SeO2The coating precursor is Se (CH)3COO)4Except that the other components and the preparation method are the same as those of the example 1.
Example 21
This example provides a spinel type cathode material, except for coating Bi2O3The coating precursor is Bi (CH)3COO)3Except that the other components and the preparation method are the same as those of the example 1.
Example 22
This example provides a spinel type cathode material except for coated Sb2O3The coating precursor is Sb (CH)3COO)3Except that the other components and the preparation method are the same as those of the example 1.
Comparative example 1
This comparative example provides a spinel type positive electrode material that is LiNi0.5Mn1.5O4The spinel type anode material is in a secondary sphere shape D50The particle size was 25 μm.
Comparative example 2
This comparative example provides a spinel type positive electrode material including Co-coated2O3LiNi of (2)0.5Mn1.5O4，Co2O3And LiNi0.5Mn1.5O4In a mass ratio of 0.5: 99.5; the spinel type anode material is in a secondary sphere shape D50The particle size was 25 μm.
Comparative example 3
This comparative example provides a spinel-type positive electrode material except SnO2And lithium nickel manganese LiNi0.5Mn1.5O4In a mass ratio of 1.5:98.5, and the rest components, the preparation method and the implementationExample 1 is the same.
The positive electrode materials obtained in examples 1 to 22 and comparative examples 1 to 3 are respectively mixed with conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride according to the mass ratio of 99:1:0.5:40:1 to prepare a positive electrode sheet, and the obtained positive electrode sheet is assembled into a 1Ah flexible package battery. The prepared positive electrode plate is rolled under the pressure of 20MPa, and the compacted density of the electrode plate can be calculated by measuring the thickness of the electrode plate; the soft-package battery is placed at 25 ℃, charged to 4.9V voltage at 0.33A rate, and discharged to 3.1V at 0.33A rate to obtain the capacity C0The volume energy density of the battery is as follows: c0X discharge plateau voltage/cell volume. The above results are shown in Table 1.
TABLE 1
From table 1, the following conclusions can be drawn:
(1) as can be seen from examples 1 to 3, 6 to 8, and 18 to 22, the spinel-type positive electrode material provided by the present invention includes a coating precursor oxide that is surface-coated and easily melted, so that lubricity of the surface of the material is increased, slip resistance between particles of the positive electrode material is reduced, and the compaction density of the prepared positive electrode sheet is increased, thereby increasing the energy density of the lithium ion battery.
(2) As can be seen from comparison between example 1 and examples 4 and 5, and between example 6 and examples 9 and 10, in the preparation method provided by the present invention, when the coating precursor is an oxide, a hydroxide, or an acetate, a positive electrode material with a high compaction density and a high energy density can be prepared, and the cycle performance of the battery is improved; when the coating precursor is acetate, the performance of the obtained cathode material is optimal.
(3) As can be seen from the comparison between examples 1 to 5 and examples 6 to 10, the positive electrode material with high compaction density and high energy density can be prepared by both of the preparation methods provided by the present invention, and the cycle performance of the battery is improved.
(4) As can be seen from comparison between example 1 and examples 11 and 12 and between example 6 and examples 13 and 14, the lithium nickel manganese oxide LiNi provided by the inventionxMn2-xO4X is more than or equal to 0.2 and less than or equal to 0.8, the surface-shaped coating oxide increases the lubricity of the surface of the material, so that the sliding resistance among particles of the anode material is reduced, and the compaction density of the prepared anode plate is increased, thereby improving the energy density of the lithium ion battery.
(3) It can be seen from the comparison between example 1 and examples 15 to 17 that, when the lithium nickel manganese oxide provided by the present invention is in the form of single crystal or secondary sphere, the positive electrode material having high compaction density and high energy density can be prepared, and the cycle performance of the battery can be improved.
(7) As can be seen from example 1 and comparative example 1, when the oxide is not coated, the prepared cathode material has low compacted density ratio and low energy density, which indicates that the coated oxide provided by the invention is beneficial to preparing the cathode material with high compacted density ratio and high energy density, and improves the cycle performance of the battery.
(8) As can be seen from example 1 and comparative example 2, when the coating oxide is not included in the oxide provided by the present invention, the prepared positive electrode material has a low compacted density ratio and a low energy density, which indicates that the oxide provided by the present invention is advantageous for preparing a positive electrode material having a high compacted density ratio and a high energy density, and improves the cycle performance of the battery.
(9) From example 1 and comparative example 3, it can be seen that when the mass ratio of the coating oxide to the lithium nickel manganese oxide is not in the range of (0.01 to 1): (99.99 to 99), the prepared positive electrode material has low compacted density ratio and low energy density, which indicates that the content of the oxide provided by the invention is beneficial to preparing the positive electrode material with high compacted density ratio and high energy density, and improving the cycle performance of the battery.
In summary, the spinel-type cathode material provided by the invention can be effectively coated by coating the oxide of the easily-melted coating precursor through two coating preparation methods of the spinel-type cathode material. The spinel type anode material has increased lubricity through coating, so that the sliding resistance among anode material particles is reduced, the compaction density of the prepared anode plate is increased, and the energy density of the lithium ion battery is improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A spinel type positive electrode material is characterized in that the spinel type positive electrode material comprises a coating oxide MOxOf lithium nickel manganese oxide, wherein
Said oxide MOxThe mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01-1) to (99.99-99);
said oxide MOxComprising B2O3、V2O5、SeO2、Sb2O3、Bi2O3Or SnO2Any one or a combination of at least two of them.
2. The spinel type positive electrode material of claim 1, wherein the lithium nickel manganese oxide has a chemical formula of LiNiyMn2-yO4Wherein y is 0.2-0.8, preferably LiNi0.5Mn1.5O4。
3. The spinel type positive electrode material according to claim 1 or 2, wherein the spinel type positive electrode material comprises a secondary sphere morphology and/or a single crystal morphology.
4. The spinel type positive electrode material according to claim 3, wherein the spinel type positive electrode material has a particle diameter D in a form of secondary spheres5018 to 35 μm;
when the spinel type anode material is in a single crystal form, the particle diameter D50Is 5 μm to 16 μm.
5. A method for producing the spinel type positive electrode material according to any one of claims 1 to 4, comprising:
mixing a lithium source, a nickel source, a manganese source and a coating precursor to obtain a mixture; and
and sintering the mixture to obtain the spinel type cathode material.
6. The method of claim 5, wherein the lithium source comprises any one of or a combination of at least two of an oxide, a hydroxide, a nitrate, an acetate, or a phosphate of lithium;
preferably, the nickel source comprises any one of or a combination of at least two of an oxide, hydroxide, nitrate, acetate or phosphate of nickel;
preferably, the manganese source comprises any one of or a combination of at least two of manganese oxide, hydroxide, nitrate, acetate or phosphate;
preferably, the coating precursor comprises any one or a combination of at least two of hydroxide, oxide or acetate of M, and the M comprises any one or a combination of at least two of B, V, Se, Sb, Bi or Sn.
7. The production method according to claim 5 or 6, wherein the temperature of the sintering is 400 ℃ to 550 ℃;
preferably, the sintering time is 12h to 32 h.
8. A method for producing the spinel type positive electrode material according to any one of claims 1 to 4, comprising:
mixing the lithium nickel manganese oxide with the coating precursor to obtain a mixture; and
and sintering the mixture to obtain the spinel type cathode material.
9. The production method according to claim 8, wherein the coating precursor includes any one of a hydroxide, an oxide, or an acetate of M or a combination of at least two thereof, the M including any one of B, V, Se, Sb, Bi, or Sn or a combination of at least two thereof;
preferably, the temperature of the sintering is 150 ℃ to 350 ℃;
preferably, the sintering time is 6 to 24 hours.
10. A positive electrode sheet for a lithium ion battery, characterized by containing the spinel-type positive electrode material according to any one of claims 1 to 4.
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