CN117747810A - Positive electrode lithium supplementing material, secondary battery and device - Google Patents
Positive electrode lithium supplementing material, secondary battery and device Download PDFInfo
- Publication number
- CN117747810A CN117747810A CN202211123628.1A CN202211123628A CN117747810A CN 117747810 A CN117747810 A CN 117747810A CN 202211123628 A CN202211123628 A CN 202211123628A CN 117747810 A CN117747810 A CN 117747810A
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- CN
- China
- Prior art keywords
- lithium
- positive electrode
- graphene
- powder
- supplementing material
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
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- 239000000292 calcium oxide Substances 0.000 description 1
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- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present application relates to a positive electrode lithium-supplementing material, and a secondary battery and a device including the same. The positive electrode lithium supplementing material comprises Li 5 M x Fe 1‑x O 4 And graphene, wherein M is at least one selected from nickel, cobalt, manganese, ruthenium, chromium, copper and aluminum, and x is more than 0 and less than 1. The positive electrode lithium supplementing material is prepared by compounding Li 5 M x Fe 1‑x O 4 And graphene, which can effectively improve the specific energy, rate capability and cycle performance of the secondary battery containing the positive electrode lithium-supplementing material.
Description
Technical Field
The present application relates to the field of energy storage. In particular, the present application relates to a positive electrode lithium supplementing material, a secondary battery including the same, and a device.
Background
Along with the increasing severity of energy crisis and environmental pollution, the demand of people for novel clean energy is also more and more urgent, wherein the new energy automobile can solve the problems of energy and emission fundamentally. In many power supply equipment, the lithium battery has the advantages of high capacity, long service life, environmental protection, good safety performance and the like, and gradually replaces other new energy batteries. In particular, lithium batteries are becoming increasingly popular as a driving force for use in electric vehicles.
However, the development of lithium battery materials and the development of preparation processes at present severely limit the development of the properties of endurance mileage, safety, quick charge and the like of electric automobiles. Especially in the first charge and discharge process of the lithium battery, the first charge and discharge efficiency is low, so that a large amount of lithium ions are lost, and the specific energy of the lithium battery is seriously influenced. Therefore, the application of the lithium supplementing technology is particularly urgent in order to improve the first efficiency of the battery.
The most common lithium supplementing technology at present is divided into negative electrode lithium supplementing and positive electrode lithium supplementing, wherein the negative electrode lithium supplementing technology mainly adopts processes such as lithium powder, lithium foil and the like to supplement irreversible capacity loss of the negative electrode in the primary charging process, and the method has the advantages of severe process conditions, high investment and great safety risk caused by the use of metal lithium. The positive electrode lithium supplementing technology mainly adds the lithium supplementing material in the mixing process, and does not need to change the process and equipment of the battery.
Li 5 FeO 4 The theoretical charging specific capacity of the material is up to 700mAh/g, and the specific discharge capacity is very small, so that Li in the first charge and discharge of the lithium battery can be supplemented + Is a loss of (2). But pure Li 5 FeO 4 The material is difficult to prepare, has a plurality of impurities, has low conductivity, has poor processability in the preparation process of the lithium ion electrode, and is easy to absorb water to form gel, thereby influencing the subsequent lithium supplementing effect.
Disclosure of Invention
In view of the shortcomings of the prior art, the application provides a positive electrode lithium supplementing material, a secondary battery comprising the positive electrode lithium supplementing material and a related device. The positive electrode lithium supplementing material is prepared by compounding Li 5 M x Fe 1-x O 4 And graphene, which can effectively improve the specific energy, rate capability and cycle performance of the secondary battery containing the positive electrode lithium-supplementing material.
A first aspect of the present application provides a positive electrode lithium supplementing material comprising Li 5 M x Fe 1-x O 4 And graphene, wherein M is at least one selected from nickel, cobalt, manganese, ruthenium, chromium, copper and aluminum, and x is more than 0 and less than 1.
A second aspect of the present application provides a method for preparing the positive electrode lithium-supplementing material according to the first aspect, which includes the following steps:
s S1: mixing a lithium source, an iron source, an M source, graphene, a complexing agent and a solvent to obtain a first mixed solution;
s2: removing the solvent in the first mixed solution to obtain first powder;
s3: carrying out first roasting treatment on the first powder to obtain second powder;
s4: and performing second roasting treatment on the second powder to obtain the positive electrode lithium supplementing material.
A third aspect of the present application provides a secondary battery comprising a positive electrode including a positive electrode active material layer including the positive electrode lithium supplementing material of the first aspect or the positive electrode lithium supplementing material prepared by the preparation method of the second aspect.
A fourth aspect of the present application provides an apparatus comprising the secondary battery according to the third aspect.
The beneficial effects of this application are:
the positive electrode lithium supplementing material provided by the application is prepared by compounding Li 5 M x Fe 1-x O 4 And graphene, on the one hand, li 5 M x Fe 1-x O 4 The material can effectively supplement Li in the first charge and discharge of the secondary battery + On the other hand, graphene can improve the conductivity of the material, and the graphene act cooperatively, so that the secondary battery containing the positive electrode lithium supplementing material has high specific energy and excellent cycle performance and rate performance.
Drawings
Fig. 1 is an XRD pattern of the positive electrode lithium-supplementing materials of example 1 and example 13 of the present application, wherein fig. 1-a is an XRD pattern of example 13 and fig. 1-B is an XRD pattern of example 1.
Fig. 2 is an SEM image of the positive electrode lithium-compensating materials of example 1 and example 13 of the present application, wherein the left image is an SEM image of example 1, and the right image is an SEM image of example 13.
Detailed Description
For simplicity, only a few numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
In the description herein, unless otherwise indicated, "above", "below" includes this number.
Unless otherwise indicated, terms used in the present application have well-known meanings commonly understood by those skilled in the art. Unless otherwise indicated, the numerical values of the parameters set forth in this application may be measured by various measurement methods commonly used in the art (e.g., may be tested according to the methods set forth in the examples of this application).
The list of items to which the term "at least one of," "at least one of," or other similar terms are connected may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single component or multiple components. Item B may comprise a single component or multiple components. Item C may comprise a single component or multiple components.
The present application is further described below in conjunction with the detailed description. It should be understood that these specific embodiments are presented by way of example only and are not intended to limit the scope of the present application.
1. Positive electrode lithium supplementing material
In a first aspect, the present application provides a positive electrode lithium supplementing material comprising Li5M x Fe 1-x O 4 And graphene, whichWherein M is at least one selected from nickel, cobalt, manganese, ruthenium, chromium, copper and aluminum, and x is more than 0 and less than 1. The positive electrode lithium supplementing material is prepared by compounding Li 5 M x Fe 1-x O 4 And graphene, on the one hand, li 5 M x Fe 1-x O 4 The material can effectively supplement Li in the first charge and discharge of the secondary battery + On the other hand, graphene can improve the conductivity of the material, and the graphene act cooperatively, so that the secondary battery containing the positive electrode lithium supplementing material has high specific energy and excellent cycle performance and rate performance.
In some embodiments, x is 0.03, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or any value therebetween. In some embodiments, 0.05.ltoreq.x.ltoreq.0.5. In some embodiments, 0.1.ltoreq.x.ltoreq.0.3.
In some embodiments, no LiFeO is present in the XRD pattern of the positive electrode lithium-supplementing material 2 Diffraction peaks of the crystalline phase. In some embodiments, the positive electrode lithium-supplementing material has an XRD spectrum without diffraction peaks in the range of 46 DEG to 50 DEG, 55 DEG to 60 DEG, and 61 DEG to 65 DEG 2 theta. In the present application, diffraction peaks in the range of 6 ° to 50 °, 55 ° to 60 °, and 61 ° to 65 ° represent LiFeO 2 Diffraction peaks of the crystalline phase. The term "absent" as used herein refers to LiFeO 2 The mass content of the crystalline phase in the positive electrode lithium supplementing material is lower than 1%.
In some embodiments, the D50 of the positive electrode lithium-compensating material is 1 μm to 5 μm. In some embodiments, the D50 of the positive electrode lithium-compensating material is 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, or any value in between.
In some embodiments, the graphene is present in an amount of 0.5% to 5% by mass based on the mass of the positive electrode lithium-compensating material. In some embodiments, the graphene is 0.7%, 1.0%, 1.3%, 1.5%, 1.7%, 2.0%, 2.3%, 2.5%, 2.7%, 3.0%, 3.3%, 3.5%, 3.7%, 4.0%, 4.3%, 4.5%, 4.7% or any value therebetween by mass. The mass content of the graphene is too highThe specific capacity of the whole material is reduced. The content is too low to reach the coating of Li 5 M x Fe 1-x O 4 And too low a content thereof also lowers Li 5 M x Fe 1-x O 4 The conductivity of the graphene material, thereby influencing the performances such as multiplying power and the like.
2. Preparation method of positive electrode lithium supplementing material
In a second aspect, the present application provides a method for preparing the positive electrode lithium-supplementing material according to the first aspect, which includes the following steps:
S1: mixing a lithium source, an iron source, an M source, graphene, a complexing agent and a solvent to obtain a first mixed solution;
s2: removing the solvent in the first mixed solution to obtain first powder;
s3: carrying out first roasting treatment on the first powder to obtain second powder;
s4: and performing second roasting treatment on the second powder to obtain the positive electrode lithium supplementing material.
In some embodiments, the complexing agent is selected from at least one of a C6-C20 carboxylic acid or a poly C6-C20 carboxylic acid. In some embodiments, the complexing agent is selected from at least one of citric acid, polyacrylic acid, or tetradecanoic acid. According to the method, the carboxylic acid or polycarboxylic acid complexing agent is added, so that the first mixed liquid obtained by the lithium source, the iron source, the M source and the graphene is more uniformly dispersed, and the obtained particles of the first powder and the second powder are more uniform and are free from agglomeration in the sintering process.
In some embodiments, the lithium source is selected from at least one of soluble lithium salts. In some embodiments, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, or lithium sulfate.
In some embodiments, the iron source is selected from at least one of soluble iron salts. In some embodiments, the iron source is selected from at least one of iron nitrate, iron sulfate, iron chloride, iron carbonate, or iron acetate.
In some embodiments, the M source is selected from at least one of soluble M salts, M is selected from at least one of nickel, cobalt, manganese, ruthenium, chromium, copper, and aluminum. In some embodiments, the M source is selected from at least one of a sulfate, nitrate, acetate, or chloride of M.
In some embodiments, the solvent is selected from at least one of water, a C1-C6 alcohol, a C6-C10 aromatic hydrocarbon, or gasoline. In some embodiments, the C1-C6 alcohol is selected from at least one of methanol, ethanol, or propanol. In some embodiments, the C6-C10 aromatic hydrocarbon is selected from at least one of benzene, toluene, or ethylbenzene.
In some embodiments, the ratio of the sum of M element and Fe element to Li element in the first mixed solution is 1: (5-6). In some embodiments, the ratio of Fe element to M element is (0.5-0.95): (0.05-0.5), for example (0.7-0.9): (0.1-0.3).
In some embodiments, the complexing agent is present in an amount of 1% -10% by mass, e.g., 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or any value therebetween, based on the total mass of the lithium source, iron source, M source, graphene, and complexing agent.
In some embodiments, the graphene is present in an amount of 0.5% -5%, such as 0.7%, 1.0%, 1.3%, 1.5%, 1.7%, 2.0%, 2.3%, 2.5%, 2.7%, 3.0%, 3.3%, 3.5%, 3.7%, 4.0%, 4.3%, 4.5%, 4.7%, or any value therebetween, based on the total mass of the lithium source, the iron source, the M source, the graphene, and the complexing agent.
In some embodiments, the temperature of the mixing is from 50 ℃ to 120 ℃. In some embodiments, the temperature of the mixing is 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or any value therebetween. In some embodiments, the mixing is for a time of 1h to 10h, such as 2h, 4h, 6h, 8h, or any value therebetween.
In some embodiments, in S3, the first calcination treatment is performed in an inert atmosphere at a temperature of 300℃to 600℃such as 350 DEG C400 ℃, 450 ℃, 500 ℃, 550 ℃, or any value therebetween. In some embodiments, in S4, the second calcination treatment is performed in an inert atmosphere at a temperature of 700 ℃ to 1000 ℃, e.g., 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, or any value therebetween. The method adopts step-by-step roasting treatment, can decompose organic matters in the first powder, and obtain Li 5 M x Fe 1-x O 4 The graphene material particles are more uniformly dispersed, no agglomeration exists, the material purity is high, no impurity phase exists, and therefore the gram capacity is high and the electrochemical performance is good.
3. Secondary battery
In a third aspect, the present application provides a secondary battery comprising a positive electrode active material layer comprising the positive electrode lithium-supplementing material of the first aspect or the positive electrode lithium-supplementing material prepared by the preparation method of the second aspect.
In some embodiments, the positive electrode lithium supplementing material has a mass content of 0.5% -5% based on the mass of the positive electrode active material layer. In some embodiments, the positive electrode lithium-compensating material is present in an amount of 0.5% -5% by mass, for example, 0.7%, 1.0%, 1.3%, 1.5%, 1.7%, 2.0%, 2.3%, 2.5%, 2.7%, 3.0%, 3.3%, 3.5%, 3.7%, 4.0%, 4.3%, 4.5%, 4.7% or any value therebetween.
In some embodiments, the positive electrode active material layer further includes a positive electrode active material, which may include one or more of lithium transition metal oxide, olivine structured lithium-containing phosphate, and their respective modified compounds. Examples of the lithium transition metal oxide may include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt aluminum oxide, and modified compounds thereof. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, one or more of lithium iron phosphate, lithium iron phosphate-carbon composites, lithium manganese phosphate-carbon composites, lithium manganese phosphate-iron, lithium manganese phosphate-carbon composites, and modified compounds thereof.
In some embodiments, the positive electrode active material layer further includes a binder, and optionally includes a conductive material. The binder enhances the bonding of the positive electrode active material particles to each other, and also enhances the bonding of the positive electrode active material to the current collector.
In some embodiments, the adhesive includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like.
In some embodiments, the conductive material includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the positive electrode further comprises a positive electrode current collector, which may be a metal foil or a composite current collector. For example, aluminum foil may be used. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, or the like) on a polymer substrate.
The positive electrode may be prepared by a preparation method well known in the art. For example, the positive electrode can be obtained by: the active material, the lithium supplementing material, the conductive material, and the binder are mixed in a solvent to prepare an active material composition, and the active material composition is coated on a current collector. In some embodiments, the solvent may include, but is not limited to: n-methylpyrrolidone.
The secondary battery of the present application further comprises a negative electrodeAnd (5) a pole. According to some embodiments of the present application, the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the current collector. In some embodiments, the anode active material layer includes an anode active material, and the specific kind of the anode active material is not particularly limited and may be selected according to the needs. Specifically, the negative electrode active material is selected from natural graphite, artificial graphite, intermediate phase micro carbon spheres (MCMB for short), hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, sn, snO, snO 2 Lithiated TiO of spinel structure 2 -Li 4 Ti 5 O 12 One or more of Li-Al alloys. Non-limiting examples of carbon materials include crystalline carbon, amorphous carbon, and mixtures thereof. The crystalline carbon may be amorphous or platelet-shaped, spherical or fibrous natural or artificial graphite. The amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, and the like.
In some embodiments, the anode active material layer further includes a binder and a conductive agent. In some embodiments, the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like.
In some embodiments, the conductive agent includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the negative electrode current collector includes: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or any combination thereof.
The negative electrode of the present application may be prepared using methods well known in the art. In general, materials such as a negative electrode active material, an optional conductive agent (for example, carbon materials such as carbon black, metal particles, and the like), a binder (for example, SBR), and other optional additives (for example, PTC thermistor materials) are mixed together and dispersed in a solvent (for example, deionized water), uniformly stirred, uniformly coated on a negative electrode current collector, and dried to obtain a negative electrode containing a negative electrode membrane. Can use metal foil or porous metal plate as negative electrode current collector
The secondary battery of the present application further includes an electrolyte. In some embodiments, the electrolyte includes a lithium salt and a solvent
In some embodiments, the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt. In some embodiments, the lithium salt includes, but is not limited to: lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium difluorophosphate (LiPO) 2 F 2 ) Lithium bis (trifluoromethanesulfonyl) imide LiN (CF) 3 SO 2 ) 2 (LiTFSI), lithium bis (fluorosulfonyl) imide Li (N (SO) 2 F) 2 ) (LiLSI), lithium bisoxalato borate LiB (C) 2 O 4 ) 2 (LiBOB) or lithium difluorooxalato borate LiBF 2 (C 2 O 4 ) (LiDFOB). In some embodiments, the concentration of lithium salt in the electrolyte is: about 0.5mol/L to 3mol/L, about 0.5mol/L to 2mol/L, or about 0.8mol/L to 1.5mol/L.
In some embodiments, the solvent may be selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), butylene Carbonate (BC), fluoroethylene carbonate (FEC), methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), sulfolane (SF), dimethylsulfone (MSM), methylsulfone (EMS), and diethylsulfone (ESE).
In some embodiments, additives are optionally also included in the electrolyte. For example, the additives may include negative electrode film-forming additives, or may include positive electrode film-forming additives, or may include additives that improve certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high temperature performance of the battery, additives that improve the low temperature performance of the battery, and the like.
The secondary battery of the present application further includes a separator. In some embodiments, a separator is provided between the positive and negative electrodes to prevent shorting. The materials and shape of the separator that can be used in the embodiments of the present application are not particularly limited, and may be any of the techniques disclosed in the prior art. In some embodiments, the separator comprises a polymer or inorganic, etc., formed from a material that is stable to the electrolyte of the present application.
For example, the release film may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer comprises at least one of polyethylene, polypropylene, polyethylene terephthalate or polyimide. Specifically, a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane can be selected.
The surface treatment layer is provided on at least one surface of the base material layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or may be a layer formed by mixing a polymer and an inorganic substance.
The inorganic layer includes inorganic particles including at least one of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or barium sulfate, and a binder. The binder comprises at least one of polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
The polymer layer contains a polymer, and the material of the polymer comprises at least one of polyamide, polyacrylonitrile, acrylic polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or poly (vinylidene fluoride-hexafluoropropylene).
According to some embodiments of the application, the secondary battery is a lithium metal secondary battery. In some embodiments, lithium metal secondary batteries include, but are not limited to: lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries.
According to some embodiments of the present application, the secondary battery may include an outer package, which may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The soft bag can be made of one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.
According to some embodiments of the present application, the shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other shape.
In some embodiments, the present application also provides a battery module. The battery module includes the secondary battery described above. The battery module of the present application employs the above-described secondary battery, and thus has at least the same advantages as the secondary battery. The number of secondary batteries contained in the battery module of the present application may be plural, and the specific number may be adjusted according to the application and capacity of the battery module.
In some embodiments, the present application also provides a battery pack including the above battery module. The number of battery modules included in the battery pack may be adjusted according to the application and capacity of the battery pack.
4. Device and method for controlling the same
The present application also provides an apparatus comprising at least one of the above secondary battery, battery module or battery pack.
In some embodiments, the apparatus includes, but is not limited to: electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric storage systems, and the like. In order to meet the high power and high energy density requirements of the device for the secondary battery, a battery pack or a battery module may be employed.
In other embodiments, the device may be a cell phone, tablet, notebook, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Examples and comparative examples
Example 1
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 5% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 2% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Example 2
Step 1): a certain amount of lithium acetate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.3:0.7, adding a certain amount of complexing agent polyacrylic acid and graphene, wherein the mass of polyacrylic acid (the weight average molecular weight of polyacrylic acid is 2000-5000 and the polymerization degree is 35-70) is 5% of the total mass (the sum of the mass of lithium carbonate, manganese acetate, ferric nitrate, polyacrylic acid and graphene). The mass of graphene is 2% of the total mass. Then adding ethanol solvent with the total mass of 150%, heating to 80 ℃ at the speed of 5 ℃/min, and fully stirring and mixing for 6 hours to uniformly mix the materials, thus obtaining mixed suspension.
Step 2): the mixed suspension was dried at 120℃and the ethanol solvent was evaporated sufficiently to obtain a xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity nitrogen protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 20h at 900 ℃ under the protection of high-purity nitrogen at the heating rate of 1 ℃/min. Obtaining Li 5 Mn 0.3 Fe 0.7 O 4 And (3) a graphene anode lithium supplementing material.
Example 3
Step 1): a certain amount of lithium acetate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.1:0.9, and then adding a certain amount of complexing agent polyacrylic acid and graphene, wherein the mass of polyacrylic acid (same as in example 2) is 5% of the total mass (sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, polyacrylic acid and graphene). The mass of graphene is 2% of the total mass. Then adding ethanol solvent with the total mass of 150%, heating to 80 ℃ at the speed of 5 ℃/min, and fully stirring and mixing for 6 hours to uniformly mix the materials, thus obtaining mixed suspension.
Step 2): the mixed suspension was dried at 120℃and the ethanol solvent was evaporated sufficiently to obtain a xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity nitrogen protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 20h at 900 ℃ under the protection of high-purity nitrogen at the heating rate of 1 ℃/min. Obtaining Li 5 Mn 0.1 Fe 0.9 O 4 And (3) a graphene anode lithium supplementing material.
Example 4
Step 1): a certain amount of lithium acetate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.4:0.6, then adding a certain amount of complexing agent polyacrylic acid and graphene, wherein the mass of polyacrylic acid (same as in example 2) is 5% of the total mass (sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, polyacrylic acid and graphene). The mass of graphene is 2% of the total mass. Then adding ethanol solvent with the total mass of 150%, heating to 80 ℃ at the speed of 5 ℃/min, and fully stirring and mixing for 6 hours to uniformly mix the materials, thus obtaining mixed suspension.
Step 2): the mixed suspension was dried at 120℃and the ethanol solvent was evaporated sufficiently to obtain a xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity nitrogen protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 20h at 900 ℃ under the protection of high-purity nitrogen at the heating rate of 1 ℃/min. Obtaining Li 5 Mn 0.4 Fe 0.6 O 4 And (3) a graphene anode lithium supplementing material.
Example 5
Step 1): a certain amount of lithium acetate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.5:0.5, and then adding a certain amount of complexing agent polyacrylic acid and graphene, wherein the mass of polyacrylic acid (same as in example 2) is 5% of the total mass (sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, polyacrylic acid and graphene). The mass of graphene is 2% of the total mass. Then adding ethanol solvent with the total mass of 150%, heating to 80 ℃ at the speed of 5 ℃/min, and fully stirring and mixing for 6 hours to uniformly mix the materials, thus obtaining mixed suspension.
Step 2): the mixed suspension was dried at 120℃and the ethanol solvent was evaporated sufficiently to obtain a xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity nitrogen protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering at 900 ℃ under the protection of high-purity nitrogen at the heating rate of 1 ℃/minAnd 0h. Obtaining Li 5 Mn 0.5 Fe 0.5 O 4 And (3) a graphene anode lithium supplementing material.
Example 6
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 5% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 0.5% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Example 7
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 5% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 1% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): fully grinding the xerogel powder, putting the powder into a muffle furnace, and heating the powder at a heating rate of 1 ℃/min under high-purity argonPresintering for 4h at 450 ℃ in protective atmosphere, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Example 8
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 5% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 3% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Example 9
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 5% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 5% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Comparative example 1
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 5% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene). And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And a positive electrode lithium supplementing material.
Example 10
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 3% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 2% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Example 11
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 7% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 2% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Example 12
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, then adding a certain amount of complexing agents of citric acid and graphene, wherein the mass of the citric acid is 9% of the total mass (the sum of the masses of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 2% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Example 13
Step 1): a certain amount of lithium carbonate, manganese acetate and ferric nitrate were weighed, li: mn: the molar ratio of Fe is 5.2:0.2:0.8, graphene is 2% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 Mn 0.2 Fe 0.8 O 4 And (3) a graphene anode lithium supplementing material.
Comparative example 2
Step 1): a certain amount of lithium carbonate and ferric nitrate was weighed, li: the molar ratio of Fe is 5.2:1, then adding a certain amount of complexing agent citric acid and graphene, wherein the mass of the citric acid is 3% of the total mass (the sum of the mass of lithium carbonate, manganese acetate, ferric nitrate, citric acid and graphene), and the mass of the graphene is 2% of the total mass. And then adding deionized water accounting for 150% of the total mass, heating to 80 ℃ at a speed of 5 ℃/min, and fully stirring and mixing for 4 hours to uniformly mix the components, thereby obtaining a mixed suspension.
Step 2): and drying the mixed suspension at 120 ℃ to fully evaporate the deionized water, thereby obtaining xerogel powder.
Step 3): and (3) fully grinding the xerogel powder, putting the powder into a muffle furnace, presintering the powder for 4 hours at 450 ℃ in a high-purity argon protective atmosphere at a heating rate of 1 ℃/min, cooling to room temperature after finishing, and grinding. Then sintering for 16h at 850 ℃ under the protection of high-purity argon at the heating rate of 1 ℃/min to obtain Li 5 FeO 4 And (3) a graphene anode lithium supplementing material. Preparation of button cell:
the lithium supplementing materials, carbon black conductive agent (SP) and binder polyvinylidene fluoride (PVDF) of the above examples and comparative examples were mixed in a weight ratio of 8:1:1, adding N-methyl pyrrolidone (NMP) accounting for 120 percent of the weight of the mixture as a solvent, mixing to prepare anode slurry, coating the slurry on an aluminum foil, and then rolling and slitting to obtain an anode plate;
assembling the battery with the positive electrode plate, PE diaphragm and negative electrode plate (lithium plate) in a stacking sequence from bottom to top, and injecting electrolyte (1 mol/L LiPF) 6 DMC (volume ratio 1:1)). Packaging on a packaging machine to obtain 2024 button cell.
Preparing a lithium ion battery:
uniformly mixing 94 parts by mass of a high-nickel ternary main material (NCM 811), 1 part by mass of a conductive agent SP, 2 parts by mass of a binder PVDF, 3 parts by mass of the lithium supplementing materials in the above examples and comparative examples and 60 parts by mass of a solvent NMP, uniformly coating the mixture on 15 mu m aluminum foil, and then rolling and slitting the mixture to obtain a positive electrode plate;
uniformly mixing 95 parts by mass of graphite main material, 1 part by mass of conductive agent SP, 1.5 parts by mass of binder SBR,1 part by mass of thickener CMC, 1 part by mass of binder PAA and 120 parts by mass of solvent deionized water, uniformly coating on a copper foil with the thickness of 8 mu m, and then rolling and slitting to obtain a negative electrode plate;
Winding the positive plate, the negative plate and the PE diaphragm to obtain a winding core, and putting intoShell, baking, pouring solution (1 mol/LLiPF) 6 DMC (volume ratio 1:1)), chemical formation and capacity division to obtain the lithium ion battery. Wherein the step of forming the component comprises the following steps: 0.05C constant current charge 120min,0.1C constant current constant voltage charge to 4.2V,0.2C discharge to 2.5V, formation is finished, high temperature standing is carried out for 24h,0.1C constant current constant voltage charge to 4.2V,0.2C constant current discharge to 2.5V,0.1C constant current constant voltage charge to 4.2V,0.2C discharge to 2.5V, and capacity division is finished.
Test method
1. XRD testing
Testing a positive electrode lithium supplementing material by adopting an X-ray powder diffractometer, wherein the target material is Cu K alpha; the voltage and current are 40KV/40mA, and the scanning angle is 10 DEG to 80 deg.
2. First time efficiency test
Charging the button cell at 25deg.C to a constant current of 0.1C and a constant voltage of 4.2V and a constant current of 4.2V to a current of 0.05C to obtain a first charge capacity, denoted as Q n Then discharging with 0.1C constant current to a voltage of 2.8V to obtain a first discharge capacity, denoted as Q m 。
First efficiency=q m /Q n ×100％
3. Specific energy test
The specific energy is calculated.
Specific energy (Wh/Kg) =capacity×average voltage/battery weight
Capacity: discharge capacity at capacity division
Mean voltage: in capacity division, the average voltage of corresponding discharge
4. Cycle performance test
Under the condition of normal temperature (25 ℃), the lithium ion battery is charged to 4.2V under the constant current and constant pressure of 0.5C, the current is cut off to 0.05C, and then the lithium ion battery is discharged to 2.5V under the constant current condition of 0.5C. After 500 cycles of charge and discharge, the capacity retention after 500 th cycle was calculated according to the following formula:
5. rate capability test
And standing for 1 hour at the constant temperature of 25 ℃, charging the lithium ion battery to 4.2V at a constant current with the multiplying power of 1C, charging the lithium ion battery at a constant voltage until the current is less than or equal to 0.05C, and standing for 30min. Then constant-current discharge is carried out to 2.5V at the rate of 1C, and the mixture is kept stand for 30min. And testing to obtain the 1C rate discharge capacity of the lithium ion battery.
And standing for 1 hour at the constant temperature of 25 ℃, charging the lithium ion battery to 4.2V at a constant current with the multiplying power of 1C, charging the lithium ion battery at a constant voltage until the current is less than or equal to 0.05C, and standing for 30min. Then constant-current discharge is carried out to 2.5V at 5C multiplying power, and the mixture is kept stand for 30min. And testing to obtain the 5C-rate discharge capacity of the lithium ion battery.
Percentage of discharge of 5 c= (5C discharge capacity/1C discharge capacity) ×100%
Test results
TABLE 1
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While certain exemplary embodiments of the present application have been illustrated and described, the present application is not limited to the disclosed embodiments. Rather, one of ordinary skill in the art will recognize that certain modifications and changes may be made to the described embodiments without departing from the spirit and scope of the present application, as described in the appended claims.
Claims (10)
1. A positive electrode lithium supplementing material comprises Li 5 M x Fe 1-x O 4 And graphene, wherein M is at least one selected from nickel, cobalt, manganese, ruthenium, chromium, copper and aluminum, and x is more than 0 and less than 1.
2. The positive electrode lithium-supplementing material according to claim 1, wherein no LiFeO is present in an XRD spectrum of the positive electrode lithium-supplementing material 2 Diffraction peaks of the crystalline phase, preferably XRD of the positive electrode lithium-supplementing materialThe spectrum has no diffraction peak in the range of 46-50 DEG, 55-60 DEG and 61-65 DEG;
and/or the D50 of the positive electrode lithium supplementing material is 1-5 μm.
3. The positive electrode lithium supplementing material according to claim 1 or 2, wherein 0.05.ltoreq.x.ltoreq.0.5, preferably 0.1.ltoreq.x.ltoreq.0.3.
4. The positive electrode lithium-supplementing material according to any one of claims 1 to 3, wherein a mass content of the graphene is 0.5% to 5% based on a mass of the positive electrode lithium-supplementing material.
5. A method for preparing the positive electrode lithium supplementing material according to any one of claims 1 to 4, comprising the steps of:
s1: mixing a lithium source, an iron source, an M source, graphene, a complexing agent and a solvent to obtain a first mixed solution;
s2: removing the solvent in the first mixed solution to obtain first powder;
s3: carrying out first roasting treatment on the first powder to obtain second powder;
S4: and performing second roasting treatment on the second powder to obtain the positive electrode lithium supplementing material.
6. The method of claim 5, wherein the complexing agent is selected from at least one of a C6-C20 carboxylic acid or a poly C6-C20 carboxylic acid, preferably at least one of citric acid, polyacrylic acid or tetradecanoic acid; and/or
The lithium source is selected from at least one of soluble lithium salts, the iron source is selected from at least one of soluble iron salts, and the M source is selected from at least one of soluble M salts; and/or
The solvent is at least one selected from water, C1-C6 alcohol, C6-C10 aromatic hydrocarbon or gasoline.
7. The method according to claim 5 or 6, wherein the ratio of the sum of M element and Fe element to Li element in the first mixed solution is 1: (5-6), the ratio of Fe element to M element is (0.5-0.95): (0.05-0.5), preferably (0.7-0.9): (0.1-0.3); and/or
Based on the total mass of the lithium source, the iron source, the M source, the graphene and the complexing agent, the mass content of the complexing agent is 1% -10%; and/or
The mass content of the graphene is 0.5% -5% based on the total mass of the lithium source, the iron source, the M source, the graphene and the complexing agent.
8. The method of any one of claims 4-7, wherein in S1, the temperature of mixing is 50 ℃ to 120 ℃; and/or
S3, performing the first roasting treatment in an inert atmosphere, wherein the temperature of the first roasting treatment is 300-600 ℃; and/or
In S4, the second roasting treatment is carried out in an inert atmosphere, and the temperature of the second roasting treatment is 700-1000 ℃.
9. A secondary battery comprising a positive electrode including a positive electrode active material layer including the positive electrode lithium-supplementing material according to any one of claims 1 to 4 or the positive electrode lithium-supplementing material prepared by the preparation method according to any one of claims 5 to 8, preferably, the positive electrode lithium-supplementing material has a mass content of 0.5% to 5% based on the mass of the positive electrode active material layer.
10. An apparatus comprising the secondary battery according to claim 9.
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| CN202211123628.1A CN117747810A (en) | 2022-09-15 | 2022-09-15 | Positive electrode lithium supplementing material, secondary battery and device |
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| CN202211123628.1A CN117747810A (en) | 2022-09-15 | 2022-09-15 | Positive electrode lithium supplementing material, secondary battery and device |
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