CN114105220B - Modified spinel type positive electrode material, preparation method thereof and lithium ion battery positive electrode sheet - Google Patents
Modified spinel type positive electrode material, preparation method thereof and lithium ion battery positive electrode sheet Download PDFInfo
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- CN114105220B CN114105220B CN202111321572.6A CN202111321572A CN114105220B CN 114105220 B CN114105220 B CN 114105220B CN 202111321572 A CN202111321572 A CN 202111321572A CN 114105220 B CN114105220 B CN 114105220B
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 106
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 103
- 239000011029 spinel Substances 0.000 title claims abstract description 103
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 55
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 54
- 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 50
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 12
- 229910013716 LiNi Inorganic materials 0.000 claims description 10
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 10
- 150000004692 metal hydroxides Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 33
- 229910052748 manganese Inorganic materials 0.000 abstract description 17
- 238000004090 dissolution Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010405 anode material Substances 0.000 description 7
- 230000005536 Jahn Teller effect Effects 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 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
- 229910018584 Mn 2-x O 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
-
- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention provides a modified spinel type positive electrode material, which comprises lithium nickel manganese oxide and doped metal oxide MO x Wherein the metal oxide MO x The mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01 to 1): 99.99 to 99; the metal oxide MO x M in (2) is in a valence state of less than two. According to the modified spinel type positive electrode material, the dissolution of manganese or the degradation of a crystal structure in a circulation process is effectively inhibited by doping the low-valence metal oxide, and the circulation stability of a battery material system is improved; according to the preparation method of the modified spinel type positive electrode material, the low-valence metal oxide precursor and the lithium nickel manganese oxide are added for co-sintering, so that the conversion from tetravalent manganese to trivalent manganese in the synthesis process is inhibited, the stability of the prepared crystal structure is improved, and the stability of a battery system is further improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a modified spinel type positive electrode material, in particular to a modified spinel type positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate.
Background
Spinel lithium nickel manganese oxide has a high reaction potential (> 4.6V) and a high theoretical specific capacity (> 140 mAh/g), and is applied to a power battery system with high energy density. However, in the charge and discharge process, the trivalent Mn element has Jahn-Teller effect, so that disproportionation reaction is easy to occur, the crystal structure is changed severely, and the charge and discharge performance of the battery is reduced greatly. Improvements in battery systems for such materials have focused on improvements in electrolytes, and there is room for improvement in the materials themselves.
How to solve the ginger-Taylor effect generated by trivalent manganese in the circulation process in a spinel lithium nickel manganese oxide material and prevent the crystal structure from being changed drastically, so that the charge and discharge performance of a battery can be improved, and the problem to be solved is a urgent need for a lithium ion battery anode material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a modified spinel type positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate, wherein metal oxide MO which is in a divalent or lower valence state is doped with metal M x In the lithium nickel manganese oxide, tetravalent manganese in the positive electrode material is restrained from being converted into trivalent manganese, so that the Jahn-Teller effect is prevented from being generated, the lattice structure is stabilized, the dissolution of manganese element is restrained, and the overall stability of the battery is improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a modified spinel positive electrode material comprising lithium nickel manganese oxide and a doped metal oxide MO x Wherein
The metal oxide MO x The mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01 to 1) (99.99 to 99);
the metal oxide MO x M in (2) is in a valence state of less than two.
The metal oxide MO x The mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01 to 1): 99.99 to 99, for example, the mass ratio can be 0.01:99.99, 0.1:99.9, 0.2:99.8, 0.5:99.5 or 1:99, but the lithium nickel manganese oxide is not limited to the listed values, and other non-listed values in the numerical range are applicable.
The modified spinel type positive electrode material provided by the invention contains the low-valence metal element with the valence state below divalent and is doped in the spinel type lithium nickel manganese oxide in an oxide form, so that tetravalent manganese can be effectively inhibited from being converted into trivalent manganese in the circulation process, the Jahn-Teller effect generated by the existence of trivalent manganese in the system is reduced, the stability of a crystal structure is improved, and the stability and the circulation performance of a battery are improved.
When doped metal oxide MO x When M in the material exceeds a divalent valence state, the transition of the valence state of manganese from tetravalent to trivalent cannot be inhibited, so that the stability of the whole material is affected.
Preferably, the lithium nickel manganese oxide has a chemical formula of LiNi y Mn 2-y O 4 Wherein, 0.2.ltoreq.y.ltoreq.0.8, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8, but the values are not limited to the cited values, and other non-cited values in the numerical range are equally applicable.
Preferably, the metal oxide MO x Combinations including any one or at least two of FeO, niO, tiO, znO, mgO, baO or SrO, typical but non-limiting combinations include FeO or NiO, niO or TiO, tiO or ZnO, znO or MgO, mgO or BaO, baO and SrO, feO, niO and TiO, znO and MgO, or ZnO, mgO, baO and SrO, preferably ZnO.
Preferably, the modified spinel-type cathode material includes a secondary sphere morphology and/or a single crystal morphology.
Preferably, the secondary sphere form of the modified spinel type positive electrode material D 50 The particle size is 20 μm to 45 μm, and may be, for example, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm or 45 μm, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the single crystal form of the modified spinel-type positive electrode material D 50 The particle size is 5 μm to 18. Mu.m, for example, 5 μm, 8 μm, 10 μm, 15 μm or 18. Mu.m, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
In a second aspect, the present invention provides a method for preparing the modified spinel-type cathode material according to the first aspect, the method comprising the steps of:
mixing lithium nickel manganese oxide with a metal oxide precursor to obtain a doping material; and
and sintering the obtained doping material to obtain the modified spinel type positive electrode material.
According to the invention, the doped metal oxide precursor and the lithium nickel manganese oxide are sintered, so that the valence state of manganese element is effectively improved in the process of synthesizing the positive electrode material, the content of trivalent manganese element in the prepared modified spinel type positive electrode material is reduced, the stability of a crystal structure is improved in the synthesis stage, and the charge and discharge performance of a battery is improved.
Preferably, the metal oxide precursor comprises any one or a combination of at least two of a metal hydroxide, a metal oxide, or a metal acetate, typically but not limited to a combination of a metal hydroxide and a metal oxide, a combination of a metal oxide and a metal acetate, a combination of a metal hydroxide and a metal acetate, or a combination of a metal hydroxide, a metal oxide, and a metal acetate.
Preferably, the sintering is performed in a nitrogen and/or inert gas atmosphere.
Preferably, the aeration flow rate of the sintering is 1Nm 3 /h to 5Nm 3 /h may be, for example, 1Nm 3 /h、2Nm 3 /h、3Nm 3 /h、4Nm 3 /h or 5Nm 3 And/h, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
In the preparation method provided by the invention, the low-valence metal oxide precursor is not oxidized to be doped by sintering under the protection of nitrogen and/or inert gas atmosphere. When the ventilation flow is greater than 5Nm 3 And/h, the constant reaction temperature can be influenced, and the synthesis efficiency is reduced; when the ventilation flow is less than 1Nm 3 And/h, which affects the protection and may oxidize the low-valence metal atoms.
Preferably, the sintering temperature is 500 ℃ to 700 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the sintering time is 16h to 32h, for example, 16h, 20h, 25h, 30h or 32h, but not limited to the recited values, and other non-recited values in the range are equally applicable.
As a preferred technical scheme of the preparation method of the second aspect of the present invention, sintering the obtained dopant to obtain the modified spinel type cathode material includes: mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 And a metal oxide precursor to obtain a doping material; the flow rate was 1Nm 3 /h to 5Nm 3 Nitrogen and/or inert gas of/h, sintering the obtained doping material for 16-32 h at the temperature of 500-700 ℃ to obtain the modified spinel type positive electrode material;
the metal oxide precursor comprises any one or a combination of at least two of metal hydroxide, metal oxide or metal acetate, and typical but non-limiting combinations include a combination of metal hydroxide and metal oxide, a combination of metal oxide and metal acetate, a combination of metal hydroxide and metal acetate, or a combination of metal hydroxide, metal oxide and metal acetate.
In a third aspect, the invention provides a positive electrode sheet of a lithium ion battery, which contains the modified spinel-type positive electrode material of the first aspect.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the modified spinel type positive electrode material, the dissolution of manganese or the degradation of a crystal structure in a circulation process is effectively inhibited by doping the low-valence metal oxide, and the circulation stability of a battery material system is improved;
(2) According to the preparation method of the modified spinel type positive electrode material, the low-valence metal oxide precursor and the lithium nickel manganese oxide are added for co-sintering, so that the conversion from tetravalent manganese to trivalent manganese in the synthesis process is inhibited, the Jahn-Teller effect is reduced, the stability of the prepared crystal structure is improved, and the stability of a battery system is further improved.
Detailed Description
The conventional method for modifying spinel type materials provided by the prior art comprises the step of coating the materials by adopting non-metal oxide, so that the influence of electrolyte in the charge and discharge process is reduced, or other materials such as Mg, al, F, cr or Fe are doped into the materials, so that the materials form a more stable structure. When the lithium nickel manganese oxide positive electrode material prepared by the method is more in charge and discharge times, the problem that the specific capacity of the battery is attenuated and the cycle performance is poor exists; and trivalent manganese in the material easily causes structural changes in the cathode material, which also affects the electrochemical performance of the cathode material.
In order to solve the technical problems, the invention provides a modified spinel type positive electrode material, a preparation method thereof and a lithium ion battery positive electrode plate, and metal oxide MO which is in a divalent or lower valence state is doped with metal M x In LiNi 0.5 Mn 1.5 O 4 In the method, the conversion of tetravalent manganese in the positive electrode material to trivalent manganese is inhibited, so that the Jahn-Teller effect is prevented from being generated, the lattice structure is stabilized, the dissolution of manganese element is inhibited, and the overall stability of the battery is improved.
The present invention will be described in further detail with reference to the following specific embodiments. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides a modified spinel type positive electrode material, wherein a metal oxide TiO, tiO and lithium nickel manganese oxide LiNi are doped in the modified spinel type positive electrode material 0.5 Mn 1.5 O 4 Is 0.5:99.5 by mass; the modified spinel type positive electrode materialThe material is in the form of a secondary sphere D 50 The particle size was 30. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 With Ti (CH) 3 COO) 2 Obtaining doping materials; at 2.5Nm 3 And introducing nitrogen into the flow of/h, and sintering the obtained doping material for 24h at the temperature of 600 ℃ to obtain the modified spinel type anode material.
Example 2
The embodiment provides a modified spinel-type positive electrode material, in which a metal oxide MO is doped x The metal oxide MO x Consists of MgO and NiO with the mass ratio of 8:2, wherein the metal oxide MO is x And lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 The mass ratio of the modified spinel type positive electrode material to the modified spinel type positive electrode material is 0.2:99.8, and the modified spinel type positive electrode material is in a secondary sphere form, D 50 The particle size was 20. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 MgO and NiO to obtain doping materials; the flow rate was 3Nm 3 And (3) sintering the obtained doping material for 32 hours under the condition of 500 ℃ to obtain the modified spinel type positive electrode material.
Example 3
The embodiment provides a modified spinel-type positive electrode material, in which a metal oxide MO is doped x The metal oxide MO x Consists of BaO and SrO with the mass ratio of 3:7, wherein the metal oxide MO x And lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 The mass ratio of the modified spinel type positive electrode material to the modified spinel type positive electrode material is 0.8:99.2, and the modified spinel type positive electrode material is in a secondary sphere form, D 50 The particle size was 45. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 BaO and SrO to obtain doping materials; the flow rate was 4Nm 3 And (3) sintering the obtained doping material for 16 hours under the condition of 700 ℃ to obtain the modified spinel type anode material.
Example 4
The embodiment provides a modified spinel type positive electrode material, wherein a metal oxide ZnO is doped in the modified spinel type positive electrode material, and the metal oxide ZnO and lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 The mass ratio of the modified spinel type positive electrode material to the modified spinel type positive electrode material is 0.01:99.99, and the modified spinel type positive electrode material is in a single crystal form, D 50 The particle size was 5. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 And Zn (OH) 2 Obtaining doping materials; the flow rate was 1Nm 3 Nitrogen per h; and sintering the obtained doping material for 24 hours at the temperature of 600 ℃ to obtain the modified spinel type anode material.
Example 5
The embodiment provides a modified spinel type positive electrode material, wherein a metal oxide FeO is doped in the modified spinel type positive electrode material, and the metal oxide FeO and lithium nickel manganese oxide LiNi are mixed 0.5 Mn 1.5 O 4 The mass ratio of the modified spinel type positive electrode material to the modified spinel type positive electrode material is 1:99, and the modified spinel type positive electrode material is in a single crystal form, D 50 The particle size was 18. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 And Fe (OH) 2 Obtaining doping materials; the flow rate was 5Nm 3 And (3) sintering the obtained doping material for 24 hours under the condition of 600 ℃ to obtain the modified spinel type positive electrode material.
Example 6
This example provides a modified spinel-type positive electrode material with a degassing flow rate of 0.6m 3 Except for/h, the remaining components and the preparation method were the same as in example 1.
Example 7
This example provides a modified spinel-type positive electrode material with a degassing flow rate of 5.5m 3 Except for/h, the remaining components and the preparation method were the same as in example 1.
Example 8
The embodiment provides a modified spinel type positive electrode material except that the chemical formula of the lithium nickel manganese oxide is LiNi 0.2 Mn 1.8 O 4 Except for this, the other components and the preparation method were the same as in example 1.
Example 9
The embodiment provides a modified spinel type positive electrode material except that the chemical formula of the lithium nickel manganese oxide is LiNi 0.8 Mn 1.2 O 4 Except for this, the other components and the preparation method were the same as in example 1.
Example 10
The embodiment provides a modified spinel type positive electrode material, wherein metal oxide ZnO, znO and lithium nickel manganese oxide LiNi are doped in the modified spinel type positive electrode material 0.5 Mn 1.5 O 4 Is 0.5:99.5 by mass; the modified spinel type positive electrode material is in a secondary sphere form, D 50 The particle size was 30. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 With Zn (CH) 3 COO) 2 Obtaining doping materials; the flow rate was 2.5Nm 3 And (3) sintering the obtained doping material for 24 hours under the condition of 600 ℃ to obtain the modified spinel type positive electrode material.
Example 11
The embodiment provides a modified spinel type positive electrode material, wherein a metal oxide ZnO is doped in the modified spinel type positive electrode material, and the metal oxide ZnO and lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 The mass ratio of the modified spinel type positive electrode material to the modified spinel type positive electrode material is 0.2:99.8, and the modified spinel type positive electrode material is in a secondary sphere form, D 50 The particle size was 20. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 And ZnO to obtain a doping material; the flow rate was 3Nm 3 And (3) sintering the obtained doping material for 32 hours under the condition of 500 ℃ to obtain the modified spinel type positive electrode material.
Example 12
The embodiment provides a modified spinel type positive electrode material, wherein a metal oxide ZnO is doped in the modified spinel type positive electrode material, and the metal oxide ZnO and lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 The mass ratio of the modified spinel type positive electrode material to the modified spinel type positive electrode material is 0.8:99.2, and the modified spinel type positive electrode material is in a secondary sphere form, D 50 The particle size was 45. Mu.m.
The preparation method of the modified spinel type positive electrode material comprises the following steps:
mixed lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 Mixing with ZnO to obtain a doping material; the flow rate was 4Nm 3 And (3) sintering the obtained doping material for 16 hours under the condition of 700 ℃ to obtain the modified spinel type anode material.
Example 13
The embodiment provides a modified spinel type positive electrode material, except that the modified spinel type positive electrode material is in a single crystal form, D 50 The other components and preparation method were the same as in example 1 except that the particle diameter was 18. Mu.m.
Example 14
The embodiment provides a modified spinel-type positive electrode material, except that the modified spinel-type positive electrode material is in a secondary spherical form, D 50 The other components and preparation method were the same as in example 4 except that the particle diameter was 20. Mu.m.
Example 15
The embodiment provides a modified spinel type positive electrode material except for the mixed lithium nickel manganese oxide LiNi in the preparation method 0.5 Mn 1.5 O 4 The other components and preparation methods were the same as in example 1 except for TiO.
Example 16
The embodiment provides a modified spinel type positive electrode material except for the mixed lithium nickel manganese oxide LiNi in the preparation method 0.5 Mn 1.5 O 4 And Ti (OH) 2 Except for this, the other components and the preparation method were the same as in example 1.
Comparative example 1
The comparative example provides a modified spinel type positive electrode material, except that the doped metal oxide is TiO 2 The other components were the same as in preparation method and example 1.
Comparative example 2
The comparative example provides a modified spinel type positive electrode material, except that the doped metal oxide is Fe 2 O 3 The other components were the same as in preparation method and example 1.
Comparative example 3
This comparative example provides a lithium nickel manganese oxide positive electrode material without adding a doped metal oxide, and the remaining components are the same as the preparation method and example 1.
The positive electrode materials obtained in examples 1 to 16 and comparative examples 1 to 3 were respectively mixed with conductive carbon black, conductive carbon tubes, a nitrogen methyl pyrrolidone solvent and polyvinylidene fluoride in a mass ratio of 99:1:0.5:40:1 to prepare positive electrode sheets, and the obtained positive electrode sheets were assembled into 1Ah soft-pack batteries. After formation and aging, the material is charged and discharged at 25 ℃ with a 1C multiplying power, and the charging and discharging voltage window is 3-4.85V. After 200 weeks of circulation, the ratio of the discharge capacity to the first week is 200 weeks of capacity retention rate; taking out the positive plate, performing XRD test, and calculating the proportion of the spinel lithium nickel manganese oxide phase in the positive active material by an XRD finishing method; taking out the negative plate, and testing the content of manganese element in the plate by an inductive coupling plasma spectrum method; the above results are shown in Table 1.
TABLE 1
From the data in table 1, it can be obtained:
(1) As can be seen from examples 1 to 5, the metal oxide MOx having a valence of less than two by doping the metal M was used in LiNi 0.5 Mn 1.5 O 4 The method inhibits the conversion of tetravalent manganese in the positive electrode material into trivalent manganese and prevents the generation of Jahn-Teller effect, so that the positive electrode material with high capacity retention rate, high spinel phase ratio and less dissolution of manganese element on the negative electrode is prepared, the stability of the battery is improved, and the cycle performance of the battery is improved.
(2) As is clear from a comparison of examples 6 and 7 with example 1, when the ventilation flow rate is greater than 5Nm 3 /h or less than 1Nm 3 And in the process of/h, the prepared positive electrode material has low capacity retention rate, low spinel phase ratio and high manganese element dissolution on the negative electrode, which indicates that the ventilation flow of the protective gas provided by the invention is beneficial to preparing the positive electrode material with high capacity retention rate, high spinel phase ratio and low manganese element dissolution on the negative electrode, thereby improving the stability of the battery and improving the cycle performance of the battery.
(3) As can be seen from a comparison of examples 8 and 9 with example 1, the lithium nickel manganese oxide LiNi provided by the invention x Mn 2-x O 4 Wherein x is more than or equal to 0.3 and less than or equal to 0.7, and the anode material with high capacity retention rate, high spinel phase ratio and less dissolution of manganese element on the anode can be prepared by doping low-valence metal oxide, so that the stability of the battery is improved, and the cycle performance of the battery is improved.
(4) As can be seen from the comparison between examples 10 to 12 and example 4, the doped metal oxide ZnO and Zn provided by the invention are divalent, and the anode material with high capacity retention rate, high spinel phase ratio and less dissolution of manganese element on the anode can be prepared, so that the stability of the battery is improved, and the cycle performance of the battery is improved.
(5) As is clear from a comparison between example 13 and example 1 and a comparison between example 14 and example 4, when the modified spinel-type positive electrode material provided by the present invention is in a single crystal form and a secondary sphere form, a positive electrode material having a high capacity retention rate, a high spinel-phase ratio, and less elution of manganese element from the negative electrode can be prepared, thereby improving the stability of the battery, improving the cycle performance of the battery, and preferably in a secondary sphere form.
(6) As can be seen from comparison of examples 15 and 16 with example 1, in the preparation method provided by the invention, when the doped metal oxide precursor is hydroxide, oxide or acetate, the positive electrode material with high capacity retention rate, high spinel phase ratio and less dissolution of manganese element on the negative electrode can be prepared, the stability of the battery is improved, and the cycle performance of the battery is improved, preferably acetate.
(7) As can be seen from comparison of comparative examples 1 and 2 with example 1, when the valence state of the metal in the doped metal oxide is higher than divalent, the prepared positive electrode material has low capacity retention rate, low spinel phase ratio and high dissolution of manganese element on the negative electrode, which indicates that the metal oxide lower than divalent valence state provided by the invention is beneficial to preparing the positive electrode material with high capacity retention rate, high spinel phase ratio and less dissolution of manganese element on the negative electrode, thereby improving the stability of the battery and the cycle performance of the battery.
(8) As can be seen from comparison of comparative example 3 and example 1, when the metal oxide is not doped, the prepared positive electrode material has low capacity retention rate, low spinel phase ratio and high dissolution of manganese element on the negative electrode, which indicates that the doped metal oxide provided by the invention is beneficial to preparing the positive electrode material with high capacity retention rate, high spinel phase ratio and less dissolution of manganese element on the negative electrode, thereby improving the stability of the battery and the cycle performance of the battery.
In conclusion, the modified spinel type positive electrode material provided by the invention effectively inhibits the problems of Mn dissolution, structural degradation and the like of a spinel type lithium nickel manganese oxide material in the circulation process, improves the circulation stability of a material system, inhibits the conversion of tetravalent Mn in the material to trivalent Mn, inhibits the distortion of ginger-Taylor, stabilizes the lattice structure and further improves the stability of a battery.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (11)
1. A modified spinel type positive electrode material is characterized by comprising lithium nickel manganese oxide and doped metal oxide MO x Wherein
The metal oxide MO x The mass ratio of the lithium nickel manganese oxide to the lithium nickel manganese oxide is (0.01 to 1): 99.99 to 99;
the metal oxide MO x M in the formula (I) is in a valence state below divalent; the metal oxide MO x Doping in the form of oxide in spinel type lithium nickel manganese oxide;
the chemical formula of the lithium nickel manganese oxide is LiNi y Mn 2-y O 4 Wherein y is more than or equal to 0.2 and less than or equal to 0.8;
the modified spinel type positive electrode material comprises a secondary sphere form and/or a single crystal form;
the metal oxide MO x Including any one or a combination of at least two of FeO, niO, tiO.
2. The modified spinel type positive electrode material according to claim 1, wherein the secondary sphere form of the modified spinel type positive electrode material has D 50 The particle size is 20 μm to 45 μm.
3. The modified spinel positive electrode material according to claim 1, wherein the single-crystal modified spinel positive electrode material has D 50 The particle size is 5 μm to 18. Mu.m.
4. A method for producing the modified spinel positive electrode material according to any one of claims 1 to 3, characterized by comprising:
mixing lithium nickel manganese oxide with a metal oxide precursor to obtain a doping material; and
and sintering the obtained doping material to obtain the modified spinel type positive electrode material.
5. The method of claim 4, wherein the metal oxide precursor comprises any one or a combination of at least two of a metal hydroxide, a metal oxide, or a metal acetate.
6. The method according to claim 4, wherein the sintering is performed in a nitrogen and/or inert gas atmosphere.
7. The method according to claim 6, wherein the aeration flow rate of sintering is 1Nm 3 /h to 5Nm 3 /h。
8. The method according to claim 4, wherein the sintering temperature is 500 ℃ to 700 ℃.
9. The method of claim 4, wherein the sintering time is 16h to 32h.
10. The method according to claim 4, wherein,
sintering the obtained doping material to obtain the modified spinel type positive electrode material comprises the following steps: the flow rate was 1Nm 3 /h to 5Nm 3 Sintering the obtained doping material for 16 to 32 hours under the condition of 500 to 700 ℃ by nitrogen and/or inert gas per hour to obtain the modified spinel type positive electrode material;
the metal oxide precursor comprises any one or a combination of at least two of metal hydroxide, metal oxide or metal acetate.
11. A positive electrode sheet for a lithium ion battery, characterized in that it contains the modified spinel positive electrode material according to any one of claims 1 to 3.
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