CN118039890A - Lithium silicomolybdate material and preparation method and application thereof - Google Patents
Lithium silicomolybdate material and preparation method and application thereof Download PDFInfo
- Publication number
- CN118039890A CN118039890A CN202410075486.9A CN202410075486A CN118039890A CN 118039890 A CN118039890 A CN 118039890A CN 202410075486 A CN202410075486 A CN 202410075486A CN 118039890 A CN118039890 A CN 118039890A
- Authority
- CN
- China
- Prior art keywords
- lithium
- silicomolybdate
- precursor
- ball
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 160
- 239000000463 material Substances 0.000 title claims abstract description 154
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 32
- 239000011733 molybdenum Substances 0.000 claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 239000012686 silicon precursor Substances 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910011140 Li2C2 Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 12
- 239000011324 bead Substances 0.000 description 12
- 150000002641 lithium Chemical class 0.000 description 12
- 229910052726 zirconium Inorganic materials 0.000 description 12
- -1 molybdate compound Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery materials, in particular to a lithium silicomolybdate material and a preparation method and application thereof. The structure of the lithium silicomolybdate material is Li 4‑2xSi1‑xMoxO4, wherein x is more than 0 and less than or equal to 0.5; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62). The preparation method comprises the following steps: according to the structure of the lithium silicomolybdate material, weighing a lithium precursor, a silicon precursor and a molybdenum precursor, mixing and performing ball milling treatment; roasting the ball-milled product at 250-350 deg.c for 1-10 hr, heating to 650-750 deg.c for 1-10 hr at 2-10 deg.c/min, and cooling to room temperature. The invention also provides application of the lithium silicomolybdate material in a lithium ion battery. The novel lithium silicomolybdate material has simple preparation process and easily obtained raw materials, and the prepared material can be used as a lithium ion battery cathode, a solid electrolyte material and the like, is widely applied, and enriches a lithium ion battery material system.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a lithium silicomolybdate material and a preparation method and application thereof.
Background
In recent years, with the development of new energy automobiles, lithium ion batteries have been widely used by virtue of their high voltage, high energy density, long cycle life, low self-discharge, no pollution, and the like. The positive electrode material, the negative electrode material, the battery diaphragm and the electrolyte in the lithium ion battery are the most important components of the lithium ion battery, the cost of the lithium ion battery accounts for about 80 percent of that of the lithium ion battery, and the quality of the lithium ion battery, such as the charge and discharge rate, the capacitance and other properties, are important problems of the continuous development of the lithium ion battery at present. In the prior art, the performance of the battery is improved by processing anode and cathode materials, electrolyte and a diaphragm; the molybdate compound is considered to be used as a lithium ion battery material to improve the battery performance due to good physical and chemical properties.
Disclosure of Invention
The invention provides a novel lithium silicomolybdate material and a preparation method thereof, and the novel lithium silicomolybdate material has wide application scenes in lithium ion batteries.
The invention adopts the following technical scheme:
In one aspect, the invention provides a lithium silicomolybdate material, which has a structure of Li 4-2xSi1- xMoxO4, wherein x is more than 0 and less than or equal to 0.5; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
Further, the lithium silicomolybdate material comprises at least one of Li3.8Si0.9Mo0.1O4、Li3.6Si0.8Mo0.2O4、Li3.4Si0.7Mo0.3O4、Li3.2Si0.6Mo0.4O4、Li3Si0.5Mo0.5O4.
Further, the lithium silicomolybdate material is prepared by mixing a lithium precursor, a silicon precursor and a molybdenum precursor;
The lithium precursor is at least one selected from Li 2CO3、LiOH·H2O、Li2C2O4;
The silicon precursor is at least one selected from SiO 2, silane and organic silicon;
the molybdenum precursor is at least one selected from MoO 3, ammonium molybdate and organic molybdenum.
Further, the particle size of the lithium silicomolybdate material is 5 nm-20 mu m.
On the other hand, the invention also provides a preparation method of the lithium silicomolybdate material, which comprises the following steps:
(1) According to the structure of the lithium silicomolybdate material, weighing a lithium precursor, a silicon precursor and a molybdenum precursor, mixing and performing ball milling treatment;
(2) Roasting the ball-milled product at 250-350 deg.c for 1-10 hr, heating to 650-750 deg.c for 1-10 hr at 2-10 deg.c/min, and cooling to room temperature to obtain the lithium silicomolybdate material.
In still another aspect, the present invention provides an application of the above lithium silicomolybdate material or the lithium silicomolybdate material prepared by the above preparation method in a lithium ion battery.
Further, the lithium silicomolybdate material is used as a solid electrolyte material in a lithium ion battery.
Further, the lithium silicomolybdate material is used as a negative electrode material or a surface coating material of a negative electrode plate in a lithium ion battery.
The lithium silicomolybdate material is a novel compound material containing silicon element, molybdenum element and lithium element, has a crystal structure space group of Pnma (No. 62), is different from the traditional silicon molybdenum material and silicon lithium material, shows excellent electrochemical properties, and has excellent electrochemical properties such as cycle capacity retention rate, coulombic efficiency and the like when being used as a lithium ion battery anode material or a solid electrolyte material.
Drawings
For a clearer description of embodiments of the invention or of solutions in the prior art, the drawings which are used in the description of the embodiments or of the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a lithium silicomolybdate material prepared in example 1;
FIG. 2 is an XRD pattern of the lithium silicomolybdate material prepared in example 2;
FIG. 3 is an XRD pattern of the lithium silicomolybdate material prepared in example 3;
FIG. 4 is an XRD pattern of the lithium silicomolybdate material prepared in example 4;
FIG. 5 is an XRD pattern of the lithium silicomolybdate material prepared in example 5;
FIG. 6 is an XRD pattern of the lithium silicomolybdate material prepared in example 6;
FIG. 7 is an XRD pattern of the lithium silicomolybdate material prepared in example 7;
FIG. 8 is an XRD pattern of a lithium silicomolybdate material prepared in example 8;
FIG. 9 is an XRD pattern of a lithium silicomolybdate material prepared in comparative example 1;
FIG. 10 is an XRD pattern of a lithium silicomolybdate material prepared in comparative example 2;
FIG. 11 is an XRD pattern of a lithium silicomolybdate material prepared in comparative example 3;
FIG. 12 is an XRD pattern of a lithium silicomolybdate material prepared in comparative example 4;
Fig. 13 is a first charge-discharge curve of a lithium ion battery using the lithium silicomolybdate material prepared in example 1 as a negative electrode material at 0.5C.
Detailed Description
The following description of the embodiments of the present invention will be made more fully hereinafter with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention provides a lithium silicomolybdate material, which has a structure of Li 4-2xSi1-xMoxO4, wherein x is more than 0 and less than or equal to 0.5; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The lithium silicomolybdate material is a novel compound material containing silicon element, molybdenum element and lithium element, has a novel crystal structure different from the traditional silicon molybdenum material and silicon lithium material, shows excellent electrochemical properties, and has potential application prospect in a battery system.
Specifically, the lithium silicomolybdate material comprises at least one of Li3.8Si0.9Mo0.1O4、Li3.6Si0.8Mo0.2O4、Li3.4Si0.7Mo0.3O4、Li3.2Si0.6Mo0.4O4、Li3Si0.5Mo0.5O4.
In some embodiments of the present invention, the lithium silicomolybdate material is prepared by mixing a lithium precursor, a silicon precursor, and a molybdenum precursor;
The lithium precursor is at least one selected from Li 2CO3、LiOH·H2O、Li2C2O4;
the silicon precursor is at least one selected from SiO 2, silane and organic silicon; more specifically, the silicon precursor is at least one selected from SiO 2, methylsilane, methylsilicone oil, ethylsilicone oil, phenylsilicone oil, methylhydrogen-containing silicone oil, methylphenyl silicone oil, methylchlorophenyl silicone oil, methylethoxy silicone oil, methyltrifluoropropyl silicone oil, methylvinyl silicone oil, methylhydroxy silicone oil, vinylsilane, aminosilane, methacryloxy silane, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, and diphenyldichlorosilane.
The molybdenum precursor is at least one selected from MoO 3, ammonium molybdate and organic molybdenum; more specifically, the molybdenum precursor is at least one selected from MoO 3, ammonium molybdate, molybdenum dialkyldithiocarbamate, molybdenum amine complex, molybdenum naphthenate and molybdenum alkylsalicylate.
In some preferred embodiments of the invention, the lithium precursor is selected from Li 2CO3, the silicon precursor is selected from SiO 2, and the molybdenum precursor is selected from MoO 3.
In some embodiments of the invention, the lithium silicomolybdate material has a particle size of from 5nm to 20 μm.
On the other hand, the invention also provides a preparation method of the lithium silicomolybdate material, which comprises the following steps:
(1) According to the structure of the lithium silicomolybdate material, weighing a lithium precursor, a silicon precursor and a molybdenum precursor, mixing and performing ball milling treatment;
(2) Roasting the ball-milled product at 250-350 deg.c for 1-10 hr, heating to 650-750 deg.c for 1-10 hr at 2-10 deg.c/min, and cooling to room temperature to obtain the lithium silicomolybdate material.
In some embodiments of the invention, the ball milling time is 10 to 120 minutes; and the ball milling process further comprises the step of drying and grinding the slurry after ball milling, so that the fineness of the raw materials is ensured.
In still another aspect, the present invention provides an application of the above lithium silicomolybdate material or the lithium silicomolybdate material prepared by the above preparation method in a lithium ion battery.
In some embodiments of the invention, the lithium silicomolybdate material is used as a solid electrolyte material in a lithium ion battery.
In some embodiments of the invention, the lithium silicomolybdate material is used as a negative electrode material or a surface cladding material of a negative electrode tab in a lithium ion battery.
The following description will be made with reference to specific embodiments.
1. Lithium silicomolybdate material
Example 1
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, weighing a lithium precursor Li 2CO3, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 according to a molar ratio of 3:1:1, adding isopropanol and zirconium beads, mixing in a planetary ball mill, and performing ball milling treatment;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product for 1h at 350 ℃, then roast the ball-milled product to 750 ℃ for 3h, the integral heating rate is 5 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
Example 2
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, weighing a lithium precursor Li 2CO3, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 according to a molar ratio of 3:1:1, adding isopropanol and zirconium beads, mixing in a planetary ball mill, and drying and grinding the slurry after ball milling;
(2) And (3) roasting the ground product in a muffle furnace, wherein the roasting procedure is to roast the product for 1h at 350 ℃, then roast the product for 3h at 700 ℃, the integral heating rate is 5 ℃/min, and naturally cool the product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
Example 3
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, weighing a lithium precursor LiOH H 2 O, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 according to the molar ratio of 6:1:1, adding isopropanol and zirconium beads, mixing in a planetary ball mill, and performing ball milling treatment;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product for 1h at 350 ℃ and then roast the ball-milled product for 3h at 680 ℃, the integral heating rate is 5 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, so as to obtain the lithium silicomolybdate material.
Example 4
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3.2Si0.6Mo0.4O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3.2Si0.6Mo0.4O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3.2Si0.6Mo0.4O4, weighing a lithium precursor Li 2CO3, a silicon precursor methyl silicone oil and a molybdenum precursor alkyl salicylic acid molybdenum according to the molar ratio of 16:3:4, adding isopropanol and zirconium beads, mixing in a planetary ball mill, and performing ball milling treatment;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product at 300 ℃ for 5 hours, then to roast the ball-milled product at 650 ℃ for 1 hour, the integral heating rate is 2 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
Example 5
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3.4Si0.7Mo0.3O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3.4Si0.7Mo0.3O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3.4Si0.7Mo0.3O4, weighing a lithium precursor Li 2C2O4, a silicon precursor methylsilane and a molybdenum precursor ammonium molybdate (NH 4)2MoO4) according to a molar ratio of 17:7:3, adding isopropanol and zirconium beads, mixing in a planetary ball mill, and performing ball milling treatment;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product at 250 ℃ for 10 hours, then roast the ball-milled product at 720 ℃ for 8 hours, the integral heating rate is 10 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
Example 6
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3.6Si0.8Mo0.2O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3.6Si0.8Mo0.2O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3.6Si0.8Mo0.2O4, weighing a lithium precursor LiOH H 2 O, a silicon precursor methylsilane and a molybdenum precursor molybdenum dialkyldithiocarbamate according to the molar ratio of 18:4:1, adding isopropanol and zirconium beads, mixing in a planetary ball mill, and performing ball milling treatment;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is that the ball-milled product is roasted for 8 hours at 280 ℃, then is roasted for 6 hours at 700 ℃, the integral heating rate is 4 ℃/min, and is naturally cooled to room temperature after roasting, so that the lithium silicomolybdate material is obtained.
Example 7
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3.8Si0.9Mo0.1O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3.8Si0.9Mo0.1O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3.8Si0.9Mo0.1O4, weighing a lithium precursor Li 2C2O4, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 according to the molar ratio of 19:9:1, adding isopropanol and zirconium beads, mixing in a planetary ball mill, and performing ball milling treatment;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product at 320 ℃ for 3 hours, then to roast the ball-milled product at 660 ℃ for 10 hours, the integral heating rate is 8 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, so as to obtain the lithium silicomolybdate material.
Example 8
The embodiment provides a lithium silicomolybdate material, wherein the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, a lithium precursor Li 2SO4, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 are weighed according to a molar ratio of 3:1:1, isopropanol and zirconium beads are added and then mixed in a planetary ball mill, and ball milling treatment is carried out;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product for 1h at 350 ℃, then roast the ball-milled product to 750 ℃ for 3h, the integral heating rate is 5 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
Comparative example 1
The embodiment provides a lithium silicomolybdate material, and the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4.
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, a lithium precursor Li 2CO3, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 are weighed according to a molar ratio of 3:1:1, isopropanol and zirconium beads are added and then mixed in a planetary ball mill, and ball milling treatment is carried out;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product for 1h at 350 ℃, then roast the ball-milled product for 3h at 770 ℃, the integral heating rate is 5 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
Comparative example 2
The embodiment provides a lithium silicomolybdate material, and the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4.
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, a lithium precursor Li 2CO3, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 are weighed according to a molar ratio of 3:1:1, isopropanol and zirconium beads are added and then mixed in a planetary ball mill, and ball milling treatment is carried out;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product for 1h at 350 ℃, then roast the ball-milled product for 3h at 620 ℃, the integral heating rate is 5 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
Comparative example 3
The embodiment provides a lithium silicomolybdate material, and the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4.
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, a lithium precursor Li 2CO3, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 are weighed according to a molar ratio of 3:1:1, isopropanol and zirconium beads are added and then mixed in a planetary ball mill, and ball milling treatment is carried out;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is that the ball-milled product is roasted for 4 hours at 750 ℃, and naturally cooling the ball-milled product to room temperature after roasting, so as to obtain the lithium silicomolybdate material.
Comparative example 4
The embodiment provides a lithium silicomolybdate material, and the structure of the lithium silicomolybdate material is Li 3Si0.5Mo0.5O4.
The preparation of Li 3Si0.5Mo0.5O4 comprises the following steps:
(1) According to the structure of a lithium silicomolybdate material Li 3Si0.5Mo0.5O4, a lithium precursor Li 2CO3, a silicon precursor SiO 2 and a molybdenum precursor MoO 3 are weighed according to a molar ratio of 3:1:1, isopropanol and zirconium beads are added and then mixed in a planetary ball mill, and ball milling treatment is carried out;
(2) And (3) roasting the ball-milled product in a muffle furnace, wherein the roasting procedure is to roast the ball-milled product for 1h at 350 ℃, then roast the ball-milled product to 750 ℃ for 3h, the integral heating rate is 12 ℃/min, and naturally cooling the ball-milled product to room temperature after roasting, thus obtaining the lithium silicomolybdate material.
XRD measurements were performed on lithium silicomolybdate materials prepared in examples 1 to 8 and comparative examples 1 to 4, and the results are shown in FIGS. 1 to 12.
XRD test method: XRD test is carried out by adopting a D8 advanced ECO X-ray diffractometer, the Ka line of the copper target is taken as a ray source, the voltage is 40kV, the current is 30mA, the 2 theta range of the test is 10-80 DEG, the step length is 0.02 DEG/step, and the step speed is 0.3 seconds/step.
As can be seen from fig. 1 to 12, the XRD patterns of the lithium silicomolybdate material prepared in each example have distinct characteristic peaks corresponding to Pnma crystal structures and no distinct impurities, which indicates that the corresponding lithium silicomolybdate material can be prepared by the method; in the XRD patterns of the lithium silicomolybdate materials prepared in each comparative example, impurity peaks were evident.
2. Lithium silicomolybdate material as lithium ion battery cathode material
The lithium silicomolybdate materials prepared in examples 1-8 and comparative examples 1-4 were ground into powder, respectively, the negative electrode active materials (i.e., lithium silicomolybdate materials), acetylene black and polyvinylidene fluoride (PVDF) were weighed according to a mass ratio of 8:1:1, respectively, N-methylpyrrolidone (NMP) was added, and the mixture was prepared into a slurry which was uniformly coated on a copper foil, and vacuum-dried at 80℃for 9 hours, and a nickel lead-out wire was welded with an ultrasonic welder to obtain a negative electrode.
And stacking the negative electrode plate, the diaphragm and the lithium foil, injecting electrolyte to form a button cell with a sandwich structure, and then performing constant-current charge and discharge test to obtain the first 100 circles of effective data. The test current density is 50mA/g, and the voltage range is 0.01-3V. The results are shown in Table 1.
The first-round charge and discharge test was performed at 0.5C using the lithium silicomolybdate material of example 1 as a negative electrode material in a lithium ion battery, and the results are shown in fig. 13.
TABLE 1
As can be seen from table 1, the lithium ion battery with the lithium silicomolybdate material prepared in each example as the negative electrode has a higher specific discharge capacity and good cycle stability, and the specific discharge capacity and the cycle stability are obviously deteriorated due to impurities in the comparative example. Specifically, as can be seen from the test results of example 1 and comparative examples 1 to 4, the lithium silicomolybdate material prepared by the roasting process of the invention is used as a lithium ion battery cathode material, and the battery has better coulombic efficiency and cycle capacity retention rate; as can be seen from the test results of examples 1 and 8, the battery performance is better when the prepared lithium silicomolybdate material is used as the negative electrode material by selecting a specific lithium precursor raw material. As shown in fig. 13, the lithium silicomolybdate material of example 1 was used as a negative electrode material in a lithium ion battery, which had a discharge capacity of 520mAh/g and a charge capacity of 500mAh/g during a stable cycle.
The invention has been further described with reference to specific embodiments, but it should be understood that the detailed description is not to be construed as limiting the spirit and scope of the invention, but rather as providing those skilled in the art with the benefit of this disclosure with the benefit of their various modifications to the described embodiments.
Claims (8)
1. The lithium silicomolybdate material is characterized in that the structure of the lithium silicomolybdate material is Li 4-2xSi1-xMoxO4, wherein x is more than 0 and less than or equal to 0.5; the group of crystal structure spaces of the lithium silicomolybdate material is Pnma (No. 62).
2. The lithium silicomolybdate material according to claim 1 wherein the lithium silicomolybdate material comprises at least one of Li3.8Si0.9Mo0.1O4、Li3.6Si0.8Mo0.2O4、Li3.4Si0.7Mo0.3O4、Li3.2Si0.6Mo0.4O4、Li3Si0.5Mo0.5O4.
3. The lithium silicomolybdate material according to claim 1, wherein the lithium silicomolybdate material is prepared by mixing a lithium precursor, a silicon precursor and a molybdenum precursor;
The lithium precursor is at least one selected from Li 2CO3、LiOH·H2O、Li2C2O4;
The silicon precursor is at least one selected from SiO 2, silane and organic silicon;
the molybdenum precursor is at least one selected from MoO 3, ammonium molybdate and organic molybdenum.
4. The lithium silicomolybdate material according to claim 1 wherein the particle size of the lithium silicomolybdate material is from 5nm to 20 μm.
5. The method for preparing a lithium silicomolybdate material according to any of claims 1 to 4 comprising the steps of:
(1) According to the structure of the lithium silicomolybdate material, weighing a lithium precursor, a silicon precursor and a molybdenum precursor, mixing and performing ball milling treatment;
(2) Roasting the ball-milled product at 250-350 deg.c for 1-10 hr, heating to 650-750 deg.c for 1-10 hr at 2-10 deg.c/min, and cooling to room temperature to obtain the lithium silicomolybdate material.
6. Use of the lithium silicomolybdate material according to any of claims 1 to 4 or the lithium silicomolybdate material prepared by the preparation method according to claim 5 in a lithium ion battery.
7. The use according to claim 6, wherein the lithium silicomolybdate material is used as a solid electrolyte material in a lithium ion battery.
8. The use according to claim 6, wherein the lithium silicomolybdate material is used as a negative electrode material or a surface coating material of a negative electrode tab in a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410075486.9A CN118039890A (en) | 2024-01-18 | 2024-01-18 | Lithium silicomolybdate material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410075486.9A CN118039890A (en) | 2024-01-18 | 2024-01-18 | Lithium silicomolybdate material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118039890A true CN118039890A (en) | 2024-05-14 |
Family
ID=90999717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410075486.9A Pending CN118039890A (en) | 2024-01-18 | 2024-01-18 | Lithium silicomolybdate material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118039890A (en) |
-
2024
- 2024-01-18 CN CN202410075486.9A patent/CN118039890A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6204196B2 (en) | Positive electrode active material for lithium secondary battery having total particle concentration gradient, method for producing the same, and lithium secondary battery including the same | |
| JP6003831B2 (en) | Sulfide solid electrolyte material, sulfide glass, lithium solid battery, and method for producing sulfide solid electrolyte material | |
| JP6252524B2 (en) | Method for producing positive electrode active material for solid state battery | |
| CN111864207B (en) | All-solid battery | |
| CN107665983B (en) | Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery | |
| CN110311120B (en) | Magnesium-containing silicon oxide negative electrode material for lithium ion battery and preparation method thereof | |
| JP2016143614A (en) | All-solid battery | |
| CN107681147B (en) | Preparation method and application of solid electrolyte coated modified lithium ion battery positive electrode material | |
| CN108923061B (en) | Solid electrolyte material and all-solid-state lithium battery | |
| JP2014071948A (en) | Method for producing negative electrode active material | |
| CN110311121B (en) | Lithium-containing silicon oxide negative electrode material for lithium ion battery and preparation method thereof | |
| CN111180709A (en) | Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof | |
| JP2016149270A (en) | Method of manufacturing positive material for lithium ion battery and electrode material manufactured by the same | |
| CN102315440A (en) | Spinel composite material, preparation method and application thereof | |
| JP2020514970A (en) | Positive electrode active material, method for producing the same, and lithium secondary battery including the same | |
| JP2016201342A (en) | Production method of composite active material | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| JP2020167151A (en) | Sulfide solid electrolyte, sulfide solid electrolyte precursor, all-solid-state battery and method for producing sulfide solid electrolyte | |
| CN110556523B (en) | Positive electrode mixture, all-solid-state battery, method for producing positive electrode mixture, and method for producing all-solid-state battery | |
| CN109037652B (en) | Preparation method and application of nitrogen-doped carbon-coated graded germanium structure | |
| CN114597341A (en) | Modified pre-lithiated silica material, preparation method and application thereof, and lithium ion battery | |
| CN110911733A (en) | Lithium-stable sulfide solid electrolyte, preparation method thereof and solid-state battery with solid electrolyte | |
| KR101285171B1 (en) | Method for manufacturing lithium titanium oxide, lithium titanium oxide manufactured by the same and lithium secondary battery comprising the lithium titanium oxide | |
| CN113991104B (en) | Vanadium-based material and preparation method and application thereof | |
| CN113410438B (en) | Preparation method for uniformly coating metal oxide on surface of lithium battery positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |