CN107946585B - Preparation method of manganese-magnesium-borate-doped magnesium ion battery positive electrode material - Google Patents
Preparation method of manganese-magnesium-borate-doped magnesium ion battery positive electrode material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 title claims description 20
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims description 18
- 229910001425 magnesium ion Inorganic materials 0.000 title claims description 18
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010405 anode material Substances 0.000 claims abstract description 37
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 22
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims abstract description 22
- VJNMMXJKXJXTOJ-UHFFFAOYSA-N magnesium manganese(2+) borate Chemical compound [Mg+2].[Mn+2].[O-]B([O-])[O-] VJNMMXJKXJXTOJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000008247 solid mixture Substances 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910017916 MgMn Inorganic materials 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims 3
- 229940063013 borate ion Drugs 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 15
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 229920000447 polyanionic polymer Polymers 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- -1 polytetrafluoroethylene Polymers 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 14
- 238000003825 pressing Methods 0.000 description 14
- 238000011160 research Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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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- 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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- General Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of kinds of doped magnesium manganese borate battery anode materials, wherein the kinds of doped magnesium manganese borate battery anode materials comprise magnesium nitrate, manganese nitrate, ammonium fluoride and trimethyl borate, the battery synthetic materials adopted by the invention are cheap and easily available, the components are simple, the purity of the synthesized product magnesium manganese borate is high, the battery is novel polyanion anode materials, the materials have high energy density and good cycle performance theoretically due to the fact that borate has low molar mass and small volume change rate before and after charging and discharging, and the doping modification can improve the electronic conductivity and the ionic conductivity of the materials, so that the electrochemical performance of the materials is improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of doped magnesium manganese borate battery anode materials.
Background
At present, the lithium ion battery is applied to fields in the aspects of mobile power supplies, household appliances, electric automobiles, energy storage equipment and the like, but the lithium storage capacity on the earth is not abundant, and along with the development of the lithium ion battery technology, people have greater and greater demand for lithium elements, and the lithium faces the danger of exhaustion in the near future.
Magnesium and lithium are positioned on diagonal positions of a periodic table of elements, and the two elements have many similar properties according to the diagonal rule, the magnesium has rich natural resource reserves, lower price and no pollution to the environment, and the magnesium ion battery is a high-energy density battery with great development prospect and is expected to replace a lithium ion battery to become a new -generation rechargeable battery system.
In view of the fact that the technology for studying the positive electrode material of the conventional magnesium battery is not mature, publication No. 102723479a discloses a positive electrode active material for a magnesium secondary battery and a magnesium secondary battery, which can achieve charge and discharge in the application of the magnesium secondary battery and can improve the high energy density and the characteristics of the magnesium secondary battery. However, magnesium batteries to this extent are far from meeting the increasingly complex use environment.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of doped magnesium manganese borate positive electrode materials with high energy density, high cycle performance and high conductivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
magnesium borate-doped positive electrode material for the battery comprises magnesium nitrate, manganese nitrate, ammonium fluoride and trimethyl borate.
The battery synthetic materials adopted by the invention are cheap and easily available, the components are simple, the purity of the synthesized product manganese magnesium borate is high, the battery is novel polyanion positive electrode materials, the borate has lower molar mass and smaller volume change rate before and after charge and discharge, and theoretically the material has higher energy density and better cycle performance, but the intrinsic electronic conductivity and ionic conductivity of the borate are lower, and the electrochemical performance of the battery is generally not good in the aspect of being used as the positive electrode material of the magnesium ion battery, but the invention can improve the electronic conductivity and ionic conductivity of the material by doping and modifying the crystal of the manganese magnesium borate with the fluorinion with stronger electronegativity, thereby improving the electrochemical performance of the material.
The preparation method of doped magnesium manganese borate positive electrode materials comprises the following steps:
(1) pretreatment: weighing raw materials according to the components of the anode material, respectively dissolving magnesium nitrate, manganese nitrate, ammonium fluoride and trimethyl borate, respectively measuring various dissolving solutions, mixing, and uniformly stirring to obtain a mixed solution;
(2) preparing a precursor: adding deionized water into the mixed solution, stirring to obtain a colloidal mixture, then placing the colloidal mixture into a steel tank, heating to react to obtain colloidal precipitate, drying, then pre-burning to obtain a solid mixture, and crushing the solid mixture to obtain a precursor;
(3) and (3) post-treatment: and mixing the precursor with a carbon source compound, adding a dispersing agent, ball-milling, drying, and sintering to obtain the battery anode material.
The traditional battery material not only has complex raw materials, but also has complex processing and synthesis steps and has higher requirements on the material. The process of the invention is very simple, and the magnesium manganese borate can be obtained by only a few simple steps, and the molecular formula of the magnesium manganese borate is MgMn (B)2O5)(1-x)F4xX is 0.005-0.05 and contains an octahedral anion structural unit (XO)m)n-The polyanion type compound positive electrode material has a different crystalline phase structure from other positive electrode materials and various outstanding performances determined by the structure through a three-dimensional network structure formed by strong covalent bonds and forming more highly coordinated gaps occupied by other metal ions.
Preferably, in step (1), magnesium nitrate, manganese nitrate and ammonium fluoride are dissolved in absolute ethanol, and trimethyl borate is dissolved in methanol. Magnesium nitrate, manganese nitrate and ammonium fluoride are inorganic salts, ethanol, water, organic matters and the like can be mixed in any proportion according to the similar compatibility principle, and trimethyl borate has the property biased to the organic matters and can be well dissolved by methanol.
Preferably, in the step (1), the various solutions are mixed in atomic molar ratio of Mg: mn: b: f is 1: 1: (2-2 x): and measuring 4x and x to 0.005-0.05. The raw materials are prepared in proportion and then synthesized, so that the proportion of atoms in molecules of the finally synthesized battery anode material is in a controllable range, and the battery failure caused by the change of the molecular structure is avoided.
Preferably, the volume ratio of the deionized water to the mixed solution in the step (2) is 0.9-1.1: 1. Deionized water with the volume similar to that of the mixed solution is added, so that the raw materials can be fully dispersed, main component ions can be dispersed, sufficient mutual influence among the ions can be obtained in subsequent violent stirring, and the products of primary mixing are uniformly distributed.
Preferably, the temperature in the step (2) is raised to 150 ℃ and 250 ℃, and the temperature is kept for 12-72 h. The step is completed in a stainless steel tank lined with polytetrafluoroethylene, and the polytetrafluoroethylene has stable property and can isolate other alloy elements in the steel tank, such as Fe and the like, from entering a reaction system of a battery anode material to cause material failure.
Preferably, the pre-sintering in the step (2) is performed at 200-350 ℃ for 4-24h under the protection of inert gas. The pre-sintering can remove organic solvent and inorganic water brought in the mixing of the raw materials, and the anode material is preliminarily shaped.
Preferably, the carbon source compound in the step (3) is or more of activated carbon, sucrose, glucose, polyethylene glycol and citric acid, the carbon source compound adopted by the invention is various, cheap and easily available, and the product cost can be effectively reduced on the basis of ensuring the product performance.
Preferably, the weight ratio of the carbon source compound to the precursor in the step (3) is 0.1-0.5: 1. the carbon is a common battery material and has a large specific surface area, and only a small amount of carbon source components are needed to coat the battery anode material, so that the specific surface area is increased, and the electron conduction efficiency is increased.
Preferably, the step (3) of sintering is sintering at 500-800 ℃ for 4-12h under the protection of inert gas. The secondary sintering can stabilize the tissue form of the battery anode material and eliminate internal stress, and meanwhile, the inert gas protection can avoid the failure of the surface coating carbon due to the oxidation of air.
Compared with the prior art, the invention has the following advantages:
(1) the battery anode material takes high-potential manganese ions as central atoms, so that the battery anode material has higher working potential, and the energy storage density of the material is improved.
(2) The stable polyanion borate is used as a crystal framework, and the borate has smaller molar mass and lower volume change rate before and after charge and discharge, so that the material has better cycle stability.
(3) Because the conductivity of the borate is low, the borate skeleton is doped and modified by a small amount of high electronegativity fluorine ions, so that the crystal generates partial deformation and electric field deformation, and the channel and electronic transition capacity of magnesium ions in the crystal are improved, thereby improving the conductivity of the material and the mobility of the magnesium ions.
(4) The preparation process is simple to operate, easy to control and beneficial to realizing large-scale industrial production.
Drawings
FIG. 1 shows MgMn (B), a positive electrode material for a magnesium-ion battery synthesized in example 12O5)0.98F0.08A second cycle charge and discharge curve at a charge and discharge current of 0.1C.
FIG. 2 shows MgMn (B), a positive electrode material for a magnesium-ion battery synthesized in example 32O5)0.96F0.16Charge and discharge capacity curves at charge and discharge currents of 0.1C for the first twenty weeks.
Detailed Description
The following are specific examples of the present invention, and the technical solution of the present invention is further described in , but the present invention is not limited to these examples.
Example 1
Pretreatment: weighing raw materials according to the components of the battery anode material, wherein the raw materials comprise 1.0mol of magnesium nitrate, 1.0mol of manganese nitrate, 0.08mol of ammonium fluoride and 1.96mol of trimethyl borate, respectively dissolving the magnesium nitrate, the manganese nitrate and the ammonium fluoride in absolute ethyl alcohol to prepare a solution with the concentration of 0.5mol/l, dissolving the trimethyl borate in methanol to prepare a solution with the concentration of 0.25mol/l, mixing the dissolved solutions, and uniformly stirring to obtain a mixed solution.
Preparing a precursor: adding deionized water into the mixed solution in a volume ratio of 1:1, violently stirring to obtain a colloidal mixture, then putting the colloidal mixture into a stainless steel tank lined with polytetrafluoroethylene, heating to 200 ℃, preserving heat for 48 hours to react to obtain colloidal precipitate, drying, then presintering at 300 ℃ for 8 hours under the protection of inert gas to obtain a solid mixture, and crushing the solid mixture to obtain a precursor.
And (3) post-treatment: mixing a carbon source compound polyethylene glycol and a precursor according to a weight ratio of 0.3: 1, adding a dispersing agent, ball-milling, drying, and sintering at 650 ℃ for 6 hours under the protection of inert gas to obtain the battery anode material.
And (3) finished product: the synthesized carbon-coated fluorine-doped magnesium ion battery anode material MgMn (B)2O5)0.98F0.08With acetylene black, polytetrafluoroethylene in a ratio of about 75: 15: 10, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in a vacuum oven at 90 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (2) was pressed on a copper mesh to make a research electrode. The research electrode is taken as a positive electrode, a metal magnesium strip is taken as a negative electrode, an Entek PE film is taken as a diaphragm, and 0.25mol/L Mg (AlCl)2BuEt)2The electrolyte solution is/THF, and the electrolyte solution is assembled into a CR2032 button cell in a glove box filled with argon.
Example 2
Pretreatment: weighing raw materials according to the components of the battery anode material, wherein the raw materials comprise 1.0mol of magnesium nitrate, 1.0mol of manganese nitrate, 0.09mol of ammonium fluoride and 1.98mol of trimethyl borate, respectively dissolving the magnesium nitrate, the manganese nitrate and the ammonium fluoride in absolute ethyl alcohol to prepare a solution with the concentration of 0.5mol/l, dissolving the trimethyl borate in methanol to prepare a solution with the concentration of 0.25mol/l, mixing various dissolved solutions, and uniformly stirring to obtain a mixed solution.
Preparing a precursor: adding deionized water into the mixed solution in a volume ratio of 1:1, violently stirring to obtain a colloidal mixture, then putting the colloidal mixture into a stainless steel tank lined with polytetrafluoroethylene, heating to 160 ℃, preserving heat for 72 hours to react to obtain colloidal precipitate, drying, then presintering at 250 ℃ for 8 hours under the protection of inert gas to obtain a solid mixture, and crushing the solid mixture to obtain a precursor.
And (3) post-treatment: mixing a carbon source compound citric acid and a precursor according to a weight ratio of 0.4: 1, adding a dispersing agent, ball-milling, drying, and sintering at 600 ℃ for 10 hours under the protection of inert gas to obtain the battery anode material.
And (3) finished product: the synthesized carbon-coated fluorine-doped magnesium ion battery anode material MgMn (B)2O5)0.99F0.04With acetylene black, polytetrafluoroethylene in a ratio of about 75: 15: 10, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in a vacuum oven at 90 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (2) was pressed on a copper mesh to make a research electrode. The research electrode is taken as a positive electrode, a metal magnesium strip is taken as a negative electrode, an Entek PE film is taken as a diaphragm, and 0.25mol/L Mg (AlCl)2BuEt)2The electrolyte solution is/THF, and the electrolyte solution is assembled into a CR2032 button cell in a glove box filled with argon.
Example 3
Pretreatment: weighing raw materials according to the components of the battery anode material, wherein the raw materials comprise 1.0mol of magnesium nitrate, 1.0mol of manganese nitrate, 0.16mol of ammonium fluoride and 1.92mol of trimethyl borate, respectively dissolving the magnesium nitrate, the manganese nitrate and the ammonium fluoride in absolute ethyl alcohol to prepare a solution with the concentration of 0.5mol/l, dissolving the trimethyl borate in methanol to prepare a solution with the concentration of 0.25mol/l, mixing various dissolved solutions, and uniformly stirring to obtain a mixed solution.
Preparing a precursor: adding deionized water with the volume ratio of 1:1 to the mixed solution, stirring to obtain a colloidal mixture, then placing the colloidal mixture into a stainless steel tank with a polytetrafluoroethylene lining, heating to 250 ℃, preserving heat for 12 hours to react to obtain colloidal precipitate, drying, then presintering at 350 ℃ for 4 hours under the protection of inert gas to obtain a solid mixture, and crushing the solid mixture to obtain a precursor.
And (3) post-treatment: mixing a carbon source compound sucrose and a precursor according to a weight ratio of 0.25: 1, adding a dispersing agent, ball-milling, drying, and sintering at 700 ℃ for 4 hours under the protection of inert gas to obtain the battery anode material.
And (3) finished product: the synthesized carbon-coated fluorine-doped magnesium ion batteryCell anode material MgMn (B)2O5)0.96F0.16With acetylene black, polytetrafluoroethylene in a ratio of about 75: 15: 10, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in a vacuum oven at 90 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (2) was pressed on a copper mesh to make a research electrode. The research electrode is taken as a positive electrode, a metal magnesium strip is taken as a negative electrode, an Entek PE film is taken as a diaphragm, and 0.25mol/L Mg (AlCl)2BuEt)2The electrolyte solution is/THF, and the electrolyte solution is assembled into a CR2032 button cell in a glove box filled with argon.
Example 4
Pretreatment: weighing raw materials according to the components of the battery anode material, wherein the raw materials comprise 1.0mol of magnesium nitrate, 1.0mol of manganese nitrate, 0.08mol of ammonium fluoride and 1.96mol of trimethyl borate, respectively dissolving the magnesium nitrate, the manganese nitrate and the ammonium fluoride in absolute ethyl alcohol to prepare a solution with the concentration of 0.5mol/l, dissolving the trimethyl borate in methanol to prepare a solution with the concentration of 0.25mol/l, mixing the dissolved solutions, and uniformly stirring to obtain a mixed solution.
Preparing a precursor: adding deionized water with the volume ratio of 0.9:1 to the mixed solution, stirring to obtain a colloidal mixture, then putting the colloidal mixture into a stainless steel tank with a polytetrafluoroethylene lining, heating to 150 ℃, keeping the temperature for 12 hours to react to obtain colloidal precipitate, drying, then presintering at 200 ℃ for 4 hours under the protection of inert gas to obtain a solid mixture, and crushing the solid mixture to obtain a precursor.
And (3) post-treatment: mixing carbon source compounds of activated carbon, sucrose, glucose, polyethylene glycol, citric acid and the precursor according to a weight ratio of 0.3: 1, adding a dispersing agent, ball-milling, drying, and sintering at 650 ℃ for 8 hours under the protection of inert gas to obtain the battery anode material.
And (3) finished product: the synthesized carbon-coated fluorine-doped magnesium ion battery anode material MgMn (B)2O5)0.98F0.08With acetylene black, polytetrafluoroethylene in a ratio of about 75: 15: 10, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in a vacuum oven at 90 ℃, and intercepting the film with the surface area of 1cm2Of a circular film ofOn the copper mesh, a research electrode was made. The research electrode is taken as a positive electrode, a metal magnesium strip is taken as a negative electrode, an Entek PE film is taken as a diaphragm, and 0.25mol/L Mg (AlCl)2BuEt)2The electrolyte solution is/THF, and the electrolyte solution is assembled into a CR2032 button cell in a glove box filled with argon.
Example 5
Pretreatment: weighing raw materials according to the components of the battery anode material, wherein the raw materials comprise 1.0mol of magnesium nitrate, 1.0mol of manganese nitrate, 0.09mol of ammonium fluoride and 1.98mol of trimethyl borate, respectively dissolving the magnesium nitrate, the manganese nitrate and the ammonium fluoride in absolute ethyl alcohol to prepare a solution with the concentration of 0.5mol/l, dissolving the trimethyl borate in methanol to prepare a solution with the concentration of 0.25mol/l, mixing various dissolved solutions, and uniformly stirring to obtain a mixed solution.
Preparing a precursor: adding deionized water with the volume ratio of 1.1:1 to the mixed solution, stirring to obtain a colloidal mixture, then putting the colloidal mixture into a stainless steel tank with a polytetrafluoroethylene lining, heating to 250 ℃, preserving heat for 72 hours to react to obtain colloidal precipitate, drying, then presintering at 350 ℃ for 24 hours under the protection of inert gas to obtain a solid mixture, and crushing the solid mixture to obtain a precursor.
And (3) post-treatment: mixing carbon source compounds of activated carbon, sucrose, glucose, polyethylene glycol, citric acid and the precursor according to a weight ratio of 0.3: 1, adding a dispersing agent, ball-milling, drying, and sintering at 650 ℃ for 8 hours under the protection of inert gas to obtain the battery anode material.
And (3) finished product: the synthesized carbon-coated fluorine-doped magnesium ion battery anode material MgMn (B)2O5)0.99F0.04With acetylene black, polytetrafluoroethylene in a ratio of about 75: 15: 10, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in a vacuum oven at 90 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (2) was pressed on a copper mesh to make a research electrode. The research electrode is taken as a positive electrode, a metal magnesium strip is taken as a negative electrode, an Entek PE film is taken as a diaphragm, and 0.25mol/L Mg (AlCl)2BuEt)2The electrolyte solution is/THF, and the electrolyte solution is assembled into a CR2032 button cell in a glove box filled with argon.
Example 6
Pretreatment: weighing raw materials according to the components of the battery anode material, wherein the raw materials comprise 1.0mol of magnesium nitrate, 1.0mol of manganese nitrate, 0.16mol of ammonium fluoride and 1.92mol of trimethyl borate, respectively dissolving the magnesium nitrate, the manganese nitrate and the ammonium fluoride in absolute ethyl alcohol to prepare a solution with the concentration of 0.5mol/l, dissolving the trimethyl borate in methanol to prepare a solution with the concentration of 0.25mol/l, mixing various dissolved solutions, and uniformly stirring to obtain a mixed solution.
Preparing a precursor: adding deionized water with the volume ratio of 1:1 to the mixed solution, stirring to obtain a colloidal mixture, then placing the colloidal mixture into a stainless steel tank with a polytetrafluoroethylene lining, heating to 200 ℃, preserving heat for 42h to react to obtain colloidal precipitate, drying, then presintering at 275 ℃ for 14h under the protection of inert gas to obtain a solid mixture, and crushing the solid mixture to obtain a precursor.
And (3) post-treatment: mixing carbon source compounds of activated carbon, sucrose, glucose, polyethylene glycol, citric acid and the precursor according to a weight ratio of 0.1: 1, adding a dispersing agent, ball-milling, drying, and sintering at 500 ℃ for 4 hours under the protection of inert gas to obtain the battery anode material.
And (3) finished product: the synthesized carbon-coated fluorine-doped magnesium ion battery anode material MgMn (B)2O5)0.96F0.16With acetylene black, polytetrafluoroethylene in a ratio of about 75: 15: 10, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in a vacuum oven at 90 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (2) was pressed on a copper mesh to make a research electrode. The research electrode is taken as a positive electrode, a metal magnesium strip is taken as a negative electrode, an Entek PE film is taken as a diaphragm, and 0.25mol/L Mg (AlCl)2BuEt)2The electrolyte solution is/THF, and the electrolyte solution is assembled into a CR2032 button cell in a glove box filled with argon.
Example 7
Pretreatment: weighing raw materials according to the components of the battery anode material, wherein the raw materials comprise 1.0mol of magnesium nitrate, 1.0mol of manganese nitrate, 0.08mol of ammonium fluoride and 1.96mol of trimethyl borate, respectively dissolving the magnesium nitrate, the manganese nitrate and the ammonium fluoride in absolute ethyl alcohol to prepare a solution with the concentration of 0.5mol/l, dissolving the trimethyl borate in methanol to prepare a solution with the concentration of 0.25mol/l, mixing the dissolved solutions, and uniformly stirring to obtain a mixed solution.
Preparing a precursor: adding deionized water with the volume ratio of 1:1 to the mixed solution, stirring to obtain a colloidal mixture, then placing the colloidal mixture into a stainless steel tank with a polytetrafluoroethylene lining, heating to 200 ℃, preserving heat for 42h to react to obtain colloidal precipitate, drying, then presintering at 275 ℃ for 14h under the protection of inert gas to obtain a solid mixture, and crushing the solid mixture to obtain a precursor.
And (3) post-treatment: mixing carbon source compounds of activated carbon, sucrose, glucose, polyethylene glycol, citric acid and the precursor according to a weight ratio of 0.5: 1, adding a dispersing agent, ball-milling, drying, and sintering at 800 ℃ for 12 hours under the protection of inert gas to obtain the battery anode material.
And (3) finished product: the synthesized carbon-coated fluorine-doped magnesium ion battery anode material MgMn (B)2O5)0.98F0.08With acetylene black, polytetrafluoroethylene in a ratio of about 75: 15: 10, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in a vacuum oven at 90 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (2) was pressed on a copper mesh to make a research electrode. The research electrode is taken as a positive electrode, a metal magnesium strip is taken as a negative electrode, an Entek PE film is taken as a diaphragm, and 0.25mol/L Mg (AlCl)2BuEt)2The electrolyte solution is/THF, and the electrolyte solution is assembled into a CR2032 button cell in a glove box filled with argon.
Comparative example 1
The only difference from example 1 is that the various solutions taken in comparative example 1 were, in atomic molar ratio Mg: mn: b: f is 1: 1: (2-2 x): 4x, x is 0.001.
Comparative example 2
The only difference from example 1 is that the various solutions taken in comparative example 2 were, in atomic molar ratio Mg: mn: b: f is 1: 1: (2-2 x): 4x, x is 0.1.
Comparative example 3
The only difference from example 1 is that comparative example 3 was obtained by mixing times the colloidal precipitate with the carbon source compound.
The magnesium ion battery positive electrode materials prepared in examples 1 to 7 and comparative examples 1 to 3 were tested for power density, energy density and energy density retention rate, and the results are shown in table 1:
table 1: properties of positive electrode materials for magnesium ion batteries in examples 1 to 7 and comparative examples 1 to 3
The energy density in the table is measured at a current density of 0.045-0.055A/g, and the energy density retention is measured at a current density of 19-21A/g after 9000 cycles.
Although the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (8)
1, magnesium borate-doped positive electrode material for a battery, which is characterized in that the positive electrode material comprises magnesium nitrate, manganese nitrate, ammonium fluoride and trimethyl borate;
the preparation method of the manganese-magnesium-borate-doped positive electrode material for the magnesium-ion battery comprises the following steps of:
(1) pretreatment: weighing the raw materials according to the components, respectively dissolving magnesium nitrate, manganese nitrate, trimethyl borate and ammonium fluoride, and then mixing the raw materials according to the atomic molar ratio of Mg: mn: b: f = 1: 1: (2-2 x): respectively measuring various dissolving solutions at 4x, x =0.005-0.05, mixing, and stirring uniformly to obtain a mixed solution;
(2) preparing a precursor: adding deionized water into the mixed solution, stirring to obtain a colloidal mixture, then placing the colloidal mixture into a steel tank, heating to react to obtain colloidal precipitate, drying, then pre-burning to obtain a solid mixture, and crushing the solid mixture to obtain a precursor;
(3) and (3) post-treatment: mixing the precursor with a carbon source, adding a dispersing agent, ball-milling, drying, and sintering to obtain the battery anode material, wherein the molecular formula of the anode material is MgMn (B)2O5)(1-x)F4x，x = 0.005-0.05。
2. The method for preparing kinds of doped magnesium manganese borate ion battery cathode materials according to claim 1, wherein magnesium nitrate, manganese nitrate and ammonium fluoride in step (1) are respectively dissolved in absolute ethanol, and trimethyl borate is dissolved in methanol.
3. The method for preparing kinds of doped magnesium manganese borate battery positive electrode materials according to claim 1, wherein the volume ratio of the deionized water to the mixed solution in step (2) is 0.9-1.1: 1.
4. The method for preparing kinds of doped magnesium manganese borate battery anode materials according to claim 1, wherein the temperature in step (2) is raised to 150 ℃ and 250 ℃, and the temperature is maintained for 12-72 h.
5. The method for preparing magnesium borate-doped positive electrode materials of batteries as claimed in claim 1, wherein the pre-sintering in step (2) is performed under the protection of inert gas at 200-350 ℃ for 4-24 h.
6. The method for preparing doped magnesium manganese borate battery cathode materials according to claim 1, wherein the carbon source in step (3) is or more of activated carbon, sucrose, glucose, polyethylene glycol and citric acid.
7. The method for preparing kinds of doped magnesium manganese borate ion battery cathode materials according to claim 1, wherein the weight ratio of the carbon source to the precursor in step (3) is 0.1-0.5: 1.
8. The method as claimed in claim 1, wherein the step (3) is sintering at 800 ℃ for 4-12h under the protection of inert gas.
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