CN114538459A - Preparation method of borate lithium ion battery cathode material and lithium ion battery - Google Patents
Preparation method of borate lithium ion battery cathode material and lithium ion battery Download PDFInfo
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- CN114538459A CN114538459A CN202210007721.XA CN202210007721A CN114538459A CN 114538459 A CN114538459 A CN 114538459A CN 202210007721 A CN202210007721 A CN 202210007721A CN 114538459 A CN114538459 A CN 114538459A
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- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000010406 cathode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 49
- 238000005245 sintering Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 43
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- 238000000034 method Methods 0.000 claims description 12
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- 239000002002 slurry Substances 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- -1 super P Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 15
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- 238000012360 testing method Methods 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/127—Borates of heavy metals
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
- H01M2004/027—Negative 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a borate lithium ion battery cathode material and a lithium ion battery, and the preparation method of the borate lithium ion battery cathode material comprises the steps of uniformly mixing a manganese source and a boron source in deionized water, carrying out hydrothermal treatment, and then sequentially sintering in air and a reducing atmosphere to obtain the lithium ion battery cathode material; wherein the chemical formula of the lithium ion battery negative electrode material is Mn3(BO3)2. The invention has the advantages of rich raw materials, low price, simple required equipment, environmental protection and the like, shows excellent electrochemical performance and meets the requirements of high specific capacity, low cost, environmental protection and the like of the lithium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a preparation method of a borate lithium ion battery cathode material and a lithium ion battery.
Background
With the gradual exhaustion of traditional fossil energy and the increasing serious problem of environmental pollution in the world, clean energy such as wind energy, solar energy, tidal energy, geothermal energy and the like is actively developed. However, due to its characteristics such as randomness and intermittence, it is difficult to achieve a continuous and stable energy output. Under the circumstances, development of efficient and convenient energy storage technology to meet the energy demand of human beings becomes a research hotspot worldwide.
The energy storage mode mainly includes mechanical energy storage, electrochemical energy storage, thermal energy storage, electrical energy storage, chemical energy storage and the like. Compared with other energy storage modes, the electrochemical energy storage technology has the characteristics of high efficiency, low investment, safe use, flexible application and the like, and is most in line with the development direction of current energy. Currently, nickel-metal hydride, lead-acid and lithium ion batteries are developed energy storage batteries. Among them, the lithium ion battery has the advantages of large energy density, long cycle life, high working voltage, no memory effect, small self-discharge, wide working temperature range and the like, and is widely used and praised.
The search for suitable electrode materials is an important component of the research of lithium ion batteries. In order to achieve wide applications in the field of electric vehicles and smart grids, lithium ion rechargeable batteries (LIBs) negative electrodes are required to have relatively negative potentials, high capacities, high energy densities and good rate capabilities. At present, commercial graphite negative electrodes are low due to the theoretical capacity (372mA h g)-1) The requirements for high energy density batteries are gradually becoming unsatisfied. In addition, the very low voltage plateau (0.1V vs. Li/Li) of the graphite material+) And also can cause potential safety hazards. Alloy compounds and transition metal compounds (oxides, phosphides, sulfides and nitrides) have also been extensively and intensively studied as negative electrode materials for lithium ion batteries. These materials, while having the unique advantages of high capacity, also have some fatal drawbacks. The volume change is large in the lithiation and delithiation processes, and the cycling stability is poor.
Therefore, it is necessary and important to search and synthesize suitable lithium ion battery negative electrode materials with low raw material cost and eco-friendliness.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
One of the purposes of the invention is to provide a preparation method of borate lithium ion battery cathode material, which has the advantages of abundant and cheap raw materials, simple required equipment, environmental friendliness and the like, and shows excellent electrochemical performance.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of borate lithium ion battery cathode material comprises the following steps,
uniformly mixing a manganese source and a boron source in deionized water, carrying out hydrothermal treatment, and then sequentially sintering in air and a reducing atmosphere to obtain a lithium ion battery cathode material;
wherein the chemical formula of the lithium ion battery negative electrode material is Mn3(BO3)2。
As a preferred scheme of the preparation method of the borate lithium ion battery cathode material, the preparation method comprises the following steps: the manganese source is selected from one or more of manganese oxide, manganese nitrate, manganese chloride or manganese sulfate;
the boron source is selected from one or more of diboron trioxide, boric acid, ammonium borate or phenylboronic acid.
As a preferable scheme of the preparation method of the borate lithium ion battery cathode material, the preparation method comprises the following steps: the molar ratio of the manganese source to the boron source is 3: 7-15.
As a preferable scheme of the preparation method of the borate lithium ion battery cathode material, the preparation method comprises the following steps: and carrying out hydrothermal treatment at the temperature of 150-220 ℃ for 12-24 h.
As a preferable scheme of the preparation method of the borate lithium ion battery cathode material, the preparation method comprises the following steps: sintering is sequentially carried out in air and a reducing atmosphere, the heating rate is 1-10 ℃/min, the sintering temperature is 600-800 ℃, and the sintering heat preservation time is 12-48 h;
in a reducing atmosphere, the heating rate is 1-10 ℃/min, the sintering temperature is 500-800 ℃, and the sintering heat preservation time is 3-7 h.
The invention also aims to provide the lithium ion battery cathode material obtained by the preparation method of the borate lithium ion battery cathode material, wherein the chemical formula of the lithium ion battery cathode material is Mn3(BO3)2Said Mn is3(BO3)2The crystal structure of (A) is an orthorhombic system, and belongs to the Pnmm space group.
The invention also aims to provide a preparation method of an electrode plate for a lithium ion battery, which comprises the steps of uniformly mixing an electrode material, conductive carbon and a binder, preparing slurry by taking water and ethanol as solvents, coating the slurry on a titanium foil, drying and pressing the titanium foil into a sheet shape;
the electrode material is the lithium ion battery negative electrode material.
As a preferable scheme of the method for preparing an electrode sheet for a lithium ion battery of the present invention, wherein: uniformly mixing an electrode material, conductive carbon and a binder, and mixing according to a mass ratio of 7-8: 1-2: 1;
the conductive carbon comprises one of acetylene black, super P, carbon black and Keqin black, and the binder is one of sodium carboxymethylcellulose, polyvinylidene fluoride and sodium alginate.
The invention also aims to provide a lithium ion battery, which consists of a negative electrode material, a positive electrode material, an electrolyte and a diaphragm, wherein the negative electrode material is the lithium ion battery negative electrode material.
As a preferable embodiment of the lithium ion battery of the present invention, wherein: the anode material is metal lithium, the diaphragm is a polypropylene diaphragm, and the electrolyte is 1M LiPF6The solvent is Ethylene Carbonate (EC), dimethyl carbonate (DMC) or dicarbonate in the mass ratio of 1:1:1Ethyl ester (DEC).
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel cathode material Mn of a lithium ion battery3(BO3)2Compared with the existing material, the material has the advantages of rich raw materials, low price, simple required equipment, environmental friendliness and the like, shows excellent electrochemical performance, and meets the requirements of high specific capacity, low cost, environmental friendliness of the lithium ion battery cathode material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows Mn obtained in example 1 of the present invention3(BO3)2XRD pattern of the material;
FIG. 2 shows Mn obtained in example 1 of the present invention3(BO3)2A charge-discharge curve graph of the material;
FIG. 3 shows Mn obtained in example 1 of the present invention3(BO3)2A cycle performance profile of the material;
FIG. 4 shows Mn obtained in example 1 of the present invention3(BO3)2The rate performance of the material.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
1.7490gNH4HB4O7·3H2O and 3.579gMn (NO)3)2(50 wt.% solution) was dispersed in 40ml of distilled water by continuous stirring. The resulting homogeneous transparent mixture was transferred to a 100mL polytetrafluoroethylene-sealed autoclave and heated at 220 ℃ for 24 h. The precipitate was washed several times with deionized water and ethanol and collected and dried in a forced air oven at 60 ℃ for 8 h. The powder was then sintered at 750 ℃ for 48H in an air atmosphere, in H2Sintering for 5 hours at 600 ℃ in an Ar atmosphere to obtain the product Mn3(BO3)2。
Fig. 1 is an XRD pattern of the synthesized product. All characteristic diffraction peaks of the product and orthogonal Mn with Pnn space group3(BO3)2The (JCPDS No.19-0781) phase could be well matched, indicating that Mn was successfully prepared3(BO3)2。
Mn for the obtained product3(BO3)2Carrying out electrochemical performance test, wherein the test method comprises the following steps:
the prepared synthetic product is used as a lithium ion battery cathode material, an electrode is prepared by adopting a coating method, and the raw materials are Mn in mass ratio3(BO3)2: acetylene black: sodium carboxymethylcellulose 70: 20: 10, taking water and ethanol as solvents to prepare slurry, coating the slurry on a copper foil, drying the copper foil in a forced air oven at 80 ℃ for 8 hours, and pressing the dried copper foil into a wafer with the diameter of 14mm to obtain the pole piece.
The pole piece is used for preparing the lithium ion battery by adopting the conventional means in the field, namely, the pole piece is used as a negative pole piece, and the metal lithium is used as a counter electrode; in an argon atmosphere1M LiPF in a protective glove box6And (EC/DMC/DEC,1:1:1w/w) is used as an electrolyte, Celgerd 2400 is used as a diaphragm, and the CR2016 type button cell is assembled.
The Shenzhen Xinwei BST-5V type battery tester is adopted to carry out electrochemical performance test, and the charge-discharge voltage range is 0.01V-3.0V (vs+/Li)。
FIG. 2 shows Mn3(BO3)2The negative electrode is 400mA g-1Representative galvanostatic charge-discharge curves from cycle 1 to cycle 3 at current density. It can be seen that during the first discharge, two distinct voltage plateaus were clearly observed at voltages around 0.1V and 0.4V, corresponding to Mn2 respectively+And the formation of an SEI film. A voltage plateau of about 1.5V during the first charge is classified as an oxidation process of metallic manganese. In the subsequent cycle, the discharge voltage plateau transitions from a 0.1V to a high voltage (about 1.0V) plateau. Mn can be obtained from the graph3(BO3)2The first discharge capacity and the charging specific capacity of the negative electrode are 896.2mA h g and g respectively-1And 544.4mA hr g-1The initial coulombic efficiency was 60.7%.
FIG. 3 shows Mn3(BO3)2The negative electrode is 400mA g-1The current density of (a). Mn3(BO3)2The cathode provided 538.1mA hr g after 400 cycles-1The specific capacity of (A).
FIG. 4 shows Mn3(BO3)2Rate capability of the negative electrode under different current densities. At 100, 200, 400, 800 and 1600mA g-1At current density of (2), Mn3(BO3)2The reversible capacity provided by the negative electrode was about 561, 489, 403, 325 and 250mA hg, respectively-1. Even at 3200mA g-1At high current density of (2), Mn3(BO3)2The specific capacity can still reach 191.5mA h g-1。Mn3(BO3)2The material has excellent cycle performance and rate capability.
Example 2
1.3457gNH4HB4O7·3H2O and 3.579gMn (NO)3)2(50 wt.% solution) was dispersed in 40ml of distilled water by continuous stirring. The resulting homogeneous transparent mixture was transferred to a 100mL polytetrafluoroethylene-sealed autoclave and heated at 220 ℃ for 12 h. The precipitate was washed several times with deionized water and ethanol and collected, and dried in a forced air oven at 60 ℃ for 8 h. The powder was then sintered at 750 ℃ for 48H in an air atmosphere, in H2Sintering for 5 hours at 600 ℃ in an Ar atmosphere to obtain the product Mn3(BO3)2。
The product Mn obtained is treated in accordance with the procedure of example 13(BO3)2And carrying out electrochemical performance test. The test result shows that the voltage is 400mA g in the range of 0.01-3.0V-1At test current density of (2), Mn3(BO3)2The first charge specific capacity of the material is up to 518.2mA h g-1After 400 cycles, the charging specific capacity is kept to be 490.7mA h g-1。
Example 3
2.3064gNH4HB4O7·3H2O and 3.579gMn (NO)3)2(50 wt.% solution) was dispersed in 40ml of distilled water by continuous stirring. The resulting homogeneous transparent mixture was transferred to a 100mL polytetrafluoroethylene-sealed autoclave and heated at 220 ℃ for 24 h. The precipitate was washed several times with deionized water and ethanol and collected and dried in a forced air oven at 60 ℃ for 8 h. The powder was then sintered at 750 ℃ for 24H in an air atmosphere in H2Sintering for 5 hours at 700 ℃ in an Ar atmosphere to obtain the product Mn3(BO3)2。
The product Mn obtained is treated in accordance with the procedure of example 13(BO3)2And carrying out electrochemical performance test. The test result shows that the voltage is 400mA g in the range of 0.01-3.0V-1At test current density of (2), Mn3(BO3)2The first charge specific capacity of the material is up to 528.0mA h g-1After 400 cycles, the charging specific capacity is kept to be 324.2mA h g-1。
Example 4
3.1827gNH4HB4O7·3H2O and 3.579gMn (NO)3)2(50 wt.% solution) was dispersed in 40ml of distilled water by continuous stirring. The resulting homogeneous transparent mixture was transferred to a 100mL polytetrafluoroethylene-sealed autoclave and heated at 220 ℃ for 24 h. The precipitate was washed several times with deionized water and ethanol and collected and dried in a forced air oven at 60 ℃ for 8 h. The powder was then sintered at 750 ℃ for 48H in an air atmosphere, in H2Sintering for 5 hours at 600 ℃ in an Ar atmosphere to obtain the product Mn3(BO3)2。
The product Mn obtained is treated in accordance with the procedure of example 13(BO3)2And carrying out electrochemical performance test. The test result shows that the voltage is 400mA g in the range of 0.01-3.0V-1At test current density of (2), Mn3(BO3)2The first charge specific capacity of the material is up to 539.1mA h g-1After 400 cycles, the specific charge capacity is kept to be 253.6mA h g-1。
Example 5
1.7490gNH4HB4O7·3H2O and 3.579gMn (NO)3)2(50 wt.% solution) was dispersed in 40ml of distilled water by continuous stirring. The resulting homogeneous transparent mixture was transferred to a 100mL polytetrafluoroethylene-sealed autoclave and heated at 220 ℃ for 24 h. The precipitate was washed several times with deionized water and ethanol and collected and dried in a forced air oven at 60 ℃ for 8 h. The powder was then sintered at 750 ℃ for 24H in an air atmosphere in H2Sintering for 5 hours at 500 ℃ in an Ar atmosphere to obtain the product Mn3(BO3)2。
The product Mn obtained is treated in accordance with the procedure of example 13(BO3)2And (5) carrying out electrochemical performance test. The test result shows that the voltage is 400mA g in the range of 0.01-3.0V-1At test current density of (2), Mn3(BO3)2The first charge specific capacity of the material is up to 466.2mA h g-1After 400 cycles, the specific charge capacity is kept to be 440.2mA h g-1。
Example 6
1.7490gNH4HB4O7·3H2O and 3.579gMn (NO)3)2(50 wt.% solution) was dispersed in 40ml of distilled water by continuous stirring. The resulting homogeneous transparent mixture was transferred to a 100mL polytetrafluoroethylene-sealed autoclave and heated at 220 ℃ for 12 h. The precipitate was washed several times with deionized water and ethanol and collected and dried in a forced air oven at 60 ℃ for 8 h. The powder was then sintered at 750 ℃ for 48H in an air atmosphere, in H2Sintering for 5 hours at 700 ℃ in an Ar atmosphere to obtain the product Mn3(BO3)2。
The product Mn obtained is treated in accordance with the procedure of example 13(BO3)2And carrying out electrochemical performance test. The test result shows that the voltage is 400mA g in the range of 0.01-3.0V-1At test current density of (2), Mn3(BO3)2The first charge specific capacity of the material is as high as 513.4mA h g-1After 400 cycles, the charging specific capacity is maintained to be 357.0mA h g-1。
The invention provides a novel cathode material Mn of a lithium ion battery3(BO3)2Compared with the existing material, the material has the advantages of rich raw materials, low price, simple required equipment, environmental friendliness and the like, shows excellent electrochemical performance, and meets the requirements of high specific capacity, low cost, environmental friendliness of the lithium ion battery cathode material.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of borate lithium ion battery cathode material is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
uniformly mixing a manganese source and a boron source in deionized water, carrying out hydrothermal treatment, and then sequentially sintering in air and a reducing atmosphere to obtain a lithium ion battery cathode material;
wherein the chemical formula of the lithium ion battery negative electrode material is Mn3(BO3)2。
2. The method of preparing a borate lithium ion battery negative electrode material of claim 1, wherein: the manganese source is selected from one or more of manganese oxide, manganese nitrate, manganese chloride or manganese sulfate;
the boron source is selected from one or more of diboron trioxide, boric acid, ammonium borate or phenylboronic acid.
3. The method of preparing the borate lithium ion battery negative electrode material of claim 1 or 2, wherein: the molar ratio of the manganese source to the boron source is 3: 7-15.
4. The method of preparing a borate lithium ion battery negative electrode material of claim 3, wherein: and carrying out hydrothermal treatment at the hydrothermal temperature of 150-220 ℃ for 12-24 h.
5. The method of making a borate lithium ion battery negative electrode material of any of claims 1, 2 or 4, wherein: sintering is sequentially carried out in air and a reducing atmosphere, the heating rate is 1-10 ℃/min, the sintering temperature is 600-800 ℃, and the sintering heat preservation time is 12-48 h;
in a reducing atmosphere, the heating rate is 1-10 ℃/min, the sintering temperature is 500-800 ℃, and the sintering heat preservation time is 3-7 h.
6. The lithium ion battery anode material obtained by the preparation method of the borate lithium ion battery anode material according to any one of claims 1 to 5, wherein: the chemical formula of the lithium ion battery cathode material is Mn3(BO3)2Said Mn is3(BO3)2The crystal structure of (A) is an orthorhombic system, and belongs to the Pnmm space group.
7. A preparation method of an electrode plate for a lithium ion battery is characterized by comprising the following steps: uniformly mixing an electrode material, conductive carbon and a binder, preparing slurry by taking water and ethanol as solvents, coating the slurry on a titanium foil, drying and pressing the titanium foil into a sheet shape;
wherein the electrode material is the lithium ion battery negative electrode material of claim 6.
8. The method for manufacturing an electrode sheet for a lithium ion battery according to claim 7, characterized in that: uniformly mixing an electrode material, conductive carbon and a binder, and mixing according to a mass ratio of 7-8: 1-2: 1;
the conductive carbon comprises one of acetylene black, super P, carbon black and Keqin black, and the binder is one of sodium carboxymethylcellulose, polyvinylidene fluoride and sodium alginate.
9. A lithium ion battery, characterized by: the lithium ion battery cathode material is composed of a cathode material, an anode material, electrolyte and a diaphragm, wherein the cathode material is the lithium ion battery cathode material of claim 6.
10. The lithium ion battery of claim 9, wherein: the anode material is metal lithium, the diaphragm is a polypropylene diaphragm, and the electrolyte is 1M LiPF6The solvent is EC, DMC and DEC with the mass ratio of 1:1: 1.
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