CN114538459B - Preparation method of borate lithium ion battery anode material and lithium ion battery - Google Patents
Preparation method of borate lithium ion battery anode material and lithium ion battery Download PDFInfo
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- CN114538459B CN114538459B CN202210007721.XA CN202210007721A CN114538459B CN 114538459 B CN114538459 B CN 114538459B CN 202210007721 A CN202210007721 A CN 202210007721A CN 114538459 B CN114538459 B CN 114538459B
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- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000010405 anode material Substances 0.000 title claims abstract description 30
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 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 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 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
- -1 polypropylene Polymers 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003273 ketjen black 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
- 238000003825 pressing Methods 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
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 6
- 239000000203 mixture 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
- 239000007772 electrode material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-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
- 238000011161 development Methods 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
- 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
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 230000003446 memory effect 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
- 238000011946 reduction process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a borate lithium ion battery cathode material and a lithium ion battery, wherein 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, performing hydrothermal treatment, and then sintering in air and a reducing atmosphere in sequence to obtain the lithium ion battery cathode material; wherein the chemical formula of the lithium ion battery anode material is Mn 3(BO3)2. The invention has the advantages of abundant raw materials, low price, simple required equipment, environmental protection and the like, and has excellent electrochemical performance, thereby meeting the requirements of high specific capacity, low cost, environmental protection 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 anode material and a lithium ion battery.
Background
With the gradual exhaustion of traditional fossil energy sources and the increasing serious environmental pollution problem in the global scope, clean energy sources such as wind energy, solar energy, tidal energy, geothermal energy and the like are actively developed. However, due to the characteristics of randomness, intermittence and the like, continuous and stable energy output is difficult to realize. Under such circumstances, development of efficient and convenient energy storage technologies to meet energy demands of humans has become a research hotspot worldwide.
The energy storage mode mainly comprises 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, less investment, safe use, flexible application and the like, and is most suitable for the development direction of the current energy sources. Currently, nickel-hydrogen, lead-acid and lithium ion batteries are all energy storage batteries with relatively mature development. The lithium ion battery has the advantages of high 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 favored.
The search for suitable electrode materials is an important component of lithium ion battery research. In order to realize wide application in the fields of electric automobiles and smart grids, lithium ion rechargeable batteries (LIBs) cathodes are required to have relatively negative potential, high capacity, high energy density and good rate capability. At present, commercial graphite negative electrode gradually cannot meet the requirement of a high-energy-density battery due to lower theoretical capacity (372 mA h g -1). In addition, the extremely low voltage plateau of graphite material (0.1 v vs. Li/Li +) also creates a safety hazard. Alloy compounds and transition metal compounds (oxides, phosphides, sulfides and nitrides) have also been extensively studied as negative electrode materials for lithium ion batteries. These materials, while having unique advantages such as high capacity, have some fatal drawbacks. The volume change is larger in the lithiation and delithiation processes, and the cyclic stability is poor.
Therefore, it is very necessary and important to explore and synthesize a suitable lithium ion battery anode material that is low in raw material cost and eco-friendly.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present invention has been made in view of the above and/or problems occurring in the prior art.
One of the purposes of the invention is to provide a preparation method of a borate lithium ion battery anode material, which has the advantages of abundant raw materials, low price, 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,
Uniformly mixing a manganese source and a boron source in deionized water, performing hydrothermal treatment, and then sintering in air and a reducing atmosphere in sequence to obtain a lithium ion battery anode material;
Wherein the chemical formula of the lithium ion battery anode material is Mn 3(BO3)2.
As a preferable scheme of the preparation method of the borate lithium ion battery anode 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 anode 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 anode material, the preparation method comprises the following steps: the hydrothermal treatment is carried out, the hydrothermal temperature is 150-220 ℃, and the hydrothermal time is 12-24 hours.
As a preferable scheme of the preparation method of the borate lithium ion battery anode material, the preparation method comprises the following steps: sintering is carried out in the air and the reducing atmosphere in turn, the temperature rising rate is 1-10 ℃/min, the sintering temperature is 600-800 ℃, and the sintering heat preservation time is 12-48 h;
under the reducing atmosphere, the temperature rising rate is 1-10 ℃/min, the sintering temperature is 500-800 ℃, and the sintering heat preservation time is 3-7 h.
The invention further provides the lithium ion battery anode material obtained by the preparation method of the borate lithium ion battery anode material, wherein the chemical formula of the lithium ion battery anode material is Mn 3(BO3)2, the crystal structure of Mn 3(BO3)2 is an orthorhombic system, and the lithium ion battery anode material belongs to a Pnnm space group.
The invention also aims to provide a preparation method of the electrode slice for the lithium ion battery, which comprises the steps of uniformly mixing an electrode material, conductive carbon and a binder, preparing slurry by using water and ethanol as solvents, coating the slurry on a titanium foil, drying and pressing the slurry into slices;
The electrode material is the negative electrode material of the lithium ion battery.
As a preferred scheme of the preparation method of the electrode sheet for the lithium ion battery, the invention comprises the following steps: the electrode material, the conductive carbon and the binder are uniformly mixed according to the mass ratio of 7-8:1-2:1;
The conductive carbon comprises one of acetylene black, super P, carbon black and ketjen black, and the binder is one of sodium hydroxymethyl cellulose, polyvinylidene fluoride and sodium alginate.
The invention further provides a lithium ion battery, which consists of a negative electrode material, a positive electrode material, electrolyte and a diaphragm, wherein the negative electrode material is the negative electrode material of the lithium ion battery.
As a preferred embodiment of the lithium ion battery of the present invention, wherein: the positive electrode material is lithium metal, the diaphragm is polypropylene diaphragm, the electrolyte is 1M LiPF 6, and the solvent is Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) in a mass ratio of 1:1:1.
Compared with the prior art, the invention has the following beneficial effects:
Compared with the existing materials, the novel anode material Mn 3(BO3)2 of the lithium ion battery 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 and the like of the anode material of the lithium ion battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is an XRD pattern of Mn 3(BO3)2 material prepared in example 1 of the present invention;
FIG. 2 is a charge-discharge curve of Mn 3(BO3)2 material prepared in example 1 of the present invention;
FIG. 3 is a graph showing the cycle performance of Mn 3(BO3)2 material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the rate performance of Mn 3(BO3)2 material prepared in example 1 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
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 other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be 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
1.7490GNH 4HB4O7·3H2 O and 3.579gMn (NO 3)2 (50 wt.% solution) were 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 24H the resulting precipitate was collected after several washes with deionized water and ethanol, dried in a forced air oven at 60℃for 8H the powder was then sintered at 750℃for 48H in an air atmosphere and at 600℃for 5H in an H 2/Ar atmosphere to give the product Mn 3(BO3)2.
Figure 1 is an XRD pattern of the synthesized product. All characteristic diffraction peaks of the product were well matched with the orthorhombic Mn 3(BO3)2 (JCPDS No. 19-0781) with Pnnm space groups, indicating successful preparation of Mn 3(BO3)2.
The obtained product Mn 3(BO3)2 is subjected to electrochemical performance test, and 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 mixed according to the mass ratio Mn 3(BO3)2: acetylene black: sodium hydroxymethyl cellulose = 70:20:10, water and ethanol are used as solvents to prepare slurry, the slurry is coated on copper foil, the copper foil is dried for 8 hours in a blast oven at 80 ℃, and the dried copper foil is pressed into a wafer with the diameter of 14mm to obtain the pole piece.
The pole piece is used for preparing the lithium ion battery, and the conventional means in the field are adopted, namely, the pole piece is taken as a negative pole piece, and metallic lithium is taken as a counter electrode; in an argon atmosphere-protected glove box, a CR2016 button cell was assembled using 1M LiPF 6 (EC/DMC/DEC, 1:1:1 w/w) as the electrolyte and Celgerd 2400 as the separator.
Electrochemical performance test is carried out by adopting Shenzhen Xinwei BST-5V type battery tester, and the charge-discharge voltage range is 0.01V-3.0V (vs. Li +/Li).
Fig. 2 shows a representative constant current charge-discharge curve for Mn 3(BO3)2 cathodes from cycle 1 to cycle 3 at a current density of 400mA g -1. It can be seen that two distinct voltage plateaus can be clearly observed at voltages of about 0.1V and 0.4V during the first discharge, corresponding to the reduction process of Mn2 + and the formation of the SEI film, respectively. A voltage plateau of about 1.5V during the first charge is classified as an oxidation process of manganese metal. In a subsequent cycle, the discharge voltage plateau transitions from 0.1V to a high voltage (about 1.0V) plateau. The initial coulombic efficiency of the Mn 3(BO3)2 anode was 60.7% as the initial discharge and charge specific capacities of 896.2mA h g -1 and 544.4mA h g -1, respectively, were obtained from the figures.
Fig. 3 shows the cycling stability of Mn 3(BO3)2 anode at a current density of 400mA g -1. Mn 3(BO3)2 anode provides a specific capacity of 538.1mA h g -1 after 400 cycles.
Fig. 4 shows the rate performance of Mn 3(BO3)2 cathodes at different current densities. Mn 3(BO3)2 negative electrodes provide reversible capacities of about 561, 489, 403, 325, and 250mA h g -1, respectively, at current densities of 100, 200, 400, 800, and 1600mA g -1. Even under the high current density of 3200mA g -1, the specific capacity of Mn 3(BO3)2 can still reach 191.5mA h g -1.Mn3(BO3)2, and the material has excellent cycle performance and rate performance.
Example 2
1.3457GNH 4HB4O7·3H2 O and 3.579gMn (NO 3)2 (50 wt.% solution) were 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 12H the resulting precipitate was collected after several washes with deionized water and ethanol, dried in a forced air oven at 60℃for 8H the powder was then sintered at 750℃for 48H in an air atmosphere and at 600℃for 5H in an H 2/Ar atmosphere to give the product Mn 3(BO3)2.
The electrochemical properties of the product Mn 3(BO3)2 obtained were tested in accordance with the procedure of example 1. The test result shows that the first charging specific capacity of the Mn 3(BO3)2 material reaches 518.2mA h g -1 under the test current density of 400mA g -1 in the charging and discharging range of 0.01-3.0V, and the specific charging capacity is kept to 490.7mA h g -1 after 400 times of circulation.
Example 3
2.3064GNH 4HB4O7·3H2 O and 3.579gMn (NO 3)2 (50 wt.% solution) were 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 24H the resulting precipitate was collected after several washes with deionized water and ethanol, dried in a forced air oven at 60℃for 8H the powder was then sintered at 750℃for 24H in an air atmosphere and at 700℃for 5H in an H 2/Ar atmosphere to give the product Mn 3(BO3)2.
The electrochemical properties of the product Mn 3(BO3)2 obtained were tested in accordance with the procedure of example 1. The test result shows that in the charge-discharge range of 0.01-3.0V, under the test current density of 400mA g -1, the first charge specific capacity of the Mn 3(BO3)2 material reaches 528.0mA h g -1, and after 400 cycles, the specific charge capacity is kept to be 324.2mA h g -1.
Example 4
3.1827GNH 4HB4O7·3H2 O and 3.579gMn (NO 3)2 (50 wt.% solution) were 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 24H the resulting precipitate was collected after several washes with deionized water and ethanol, dried in a forced air oven at 60℃for 8H the powder was then sintered at 750℃for 48H in an air atmosphere and at 600℃for 5H in an H 2/Ar atmosphere to give the product Mn 3(BO3)2.
The electrochemical properties of the product Mn 3(BO3)2 obtained were tested in accordance with the procedure of example 1. The test result shows that the first charging specific capacity of the Mn 3(BO3)2 material reaches 539.1mA h g -1 under the test current density of 400mA g -1 in the charging and discharging range of 0.01-3.0V, and the specific charging capacity is kept to 253.6mA h g -1 after 400 times of circulation.
Example 5
1.7490GNH 4HB4O7·3H2 O and 3.579gMn (NO 3)2 (50 wt.% solution) were 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 24H the resulting precipitate was collected after several washes with deionized water and ethanol, dried in a forced air oven at 60℃for 8H the powder was then sintered at 750℃for 24H in an air atmosphere and at 500℃for 5H in an H 2/Ar atmosphere to obtain the product Mn 3(BO3)2.
The electrochemical properties of the product Mn 3(BO3)2 obtained were tested in accordance with the procedure of example 1. The test result shows that the first charging specific capacity of the Mn 3(BO3)2 material reaches 466.2mA h g -1 under the test current density of 400mA g -1 in the charging and discharging range of 0.01-3.0V, and the specific charging capacity is kept to be 440.2mA h g -1 after 400 times of circulation.
Example 6
1.7490GNH 4HB4O7·3H2 O and 3.579gMn (NO 3)2 (50 wt.% solution) were 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 12H the resulting precipitate was collected after several washes with deionized water and ethanol, dried in a forced air oven at 60℃for 8H the powder was then sintered at 750℃for 48H in an air atmosphere and at 700℃for 5H in an H 2/Ar atmosphere to give the product Mn 3(BO3)2.
The electrochemical properties of the product Mn 3(BO3)2 obtained were tested in accordance with the procedure of example 1. The test result shows that the first charging specific capacity of the Mn 3(BO3)2 material reaches 513.4mA h g -1 under the test current density of 400mA g -1 in the charging and discharging range of 0.01-3.0V, and the specific charging capacity is kept to 357.0mA h g -1 after 400 times of circulation.
Compared with the existing materials, the novel anode material Mn 3(BO3)2 of the lithium ion battery 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 and the like of the anode material of the lithium ion battery.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, 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 the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (8)
1. A borate lithium ion battery, characterized in that: the lithium ion battery comprises a negative electrode material, a positive electrode material, electrolyte and a diaphragm, wherein the positive electrode material is metallic lithium, the diaphragm is a polypropylene diaphragm, the electrolyte is 1M LiPF 6, and the solvent is EC, DMC, DEC with a mass ratio of 1:1:1;
The chemical formula of the anode material is Mn 3(BO3)2, the crystal structure of Mn 3(BO3)2 is an orthorhombic system, and the anode material belongs to a Pnnm space group;
The borate lithium ion battery has a specific charge capacity of 466.2~544.4 mA h g -1 at a current density of 400mA g -1 in a charging and discharging range of 0.01-3.0V, and the specific charge capacity is kept to be 253.6~538.1 mA h g -1 after 400 cycles.
2. The borate lithium ion battery of claim 1, wherein: uniformly mixing a cathode material, conductive carbon and a binder, preparing slurry by using water and ethanol as solvents, coating the slurry on a titanium foil, drying and pressing the dried slurry into a sheet shape.
3. The borate lithium ion battery of claim 2, wherein: uniformly mixing the anode material, the conductive carbon and the binder according to the mass ratio of 7-8:1-2:1;
The conductive carbon comprises one of acetylene black, super P, carbon black and ketjen black, and the binder is one of sodium hydroxymethyl cellulose, polyvinylidene fluoride and sodium alginate.
4. The method for preparing the anode material of the borate lithium ion battery according to claim 1, wherein: comprising the steps of (a) a step of,
Uniformly mixing a manganese source and a boron source in deionized water, performing hydrothermal treatment, and then sintering in air and a reducing atmosphere in sequence to obtain a lithium ion battery anode material;
Wherein the chemical formula of the lithium ion battery anode material is Mn 3(BO3)2.
5. The method for preparing the borate lithium ion battery anode material according to claim 4, wherein the 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.
6. The method for preparing the borate lithium ion battery anode material according to claim 4 or 5, wherein the method comprises the following steps: the molar ratio of the manganese source to the boron source is 3:7-15.
7. The method for preparing the borate lithium ion battery anode material according to claim 6, wherein the method comprises the following steps: the hydrothermal treatment is carried out, the hydrothermal temperature is 150-220 ℃, and the hydrothermal time is 12-24 hours.
8. The method for preparing the borate lithium ion battery anode material according to any one of claims 4, 5 or 7, wherein: sintering is sequentially carried out in air and a reducing atmosphere, the temperature rising rate is 1-10 ℃/min, the sintering temperature is 600-800 ℃, and the sintering heat preservation time is 12-48 h;
under the reducing atmosphere, the temperature rising rate is 1-10 ℃/min, the sintering temperature is 500-800 ℃, and the sintering heat preservation time is 3-7 h.
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