CN114300670A - Vanadium-based glass negative electrode material, and preparation method and application thereof - Google Patents
Vanadium-based glass negative electrode material, and preparation method and application thereof Download PDFInfo
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- CN114300670A CN114300670A CN202111628611.7A CN202111628611A CN114300670A CN 114300670 A CN114300670 A CN 114300670A CN 202111628611 A CN202111628611 A CN 202111628611A CN 114300670 A CN114300670 A CN 114300670A
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- lithium ion
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- 239000011521 glass Substances 0.000 title claims abstract description 53
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 40
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 24
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 24
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 16
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 239000010405 anode material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000006060 molten glass Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 238000003917 TEM image Methods 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
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
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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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- Battery Electrode And Active Subsutance (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a vanadium-based glass negative electrode material, and a preparation method and application thereof. The vanadium-based glass negative electrode material is prepared from metal oxide, vanadium pentoxide and boron oxide; the metal oxide is selected from Fe2O3、Ga2O3、Ln2O3、MgO、ZnO、CoO、NiO、CdO、Nb2O5And Y2O3At least one of; the mass ratio of the metal oxide to the vanadium pentoxide to the boron oxide is 10-50: 40-70: 10 to 40. The invention relates to aThe vanadium-based glass negative electrode material is prepared by mixing metal oxide, vanadium pentoxide and boron oxide with specific components according to a certain proportion, and the lithium ion battery prepared from the vanadium-based glass negative electrode material has high first discharge specific capacity and excellent cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a vanadium-based glass negative electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries are considered by the general public as one of the most promising energy conversion and storage devices due to their inherent advantages, such as high energy density, high efficiency, superior rate capability and longer cycle life. The cathode is an essential key material of the lithium ion battery and plays a key role in the development of the lithium ion battery.
The metal oxide has the advantages of high lithium storage capacity, low price and easy obtainment as an electrode of a lithium ion battery, but the metal oxide has poor conductivity, and when the metal oxide is used as an electrode material of the lithium ion battery, because irreversible phase change and volume expansion can occur in the process of charging and discharging, and strain and microcrack can be caused by uneven volume expansion caused by phase change, so that obvious capacity attenuation can occur, and the cycling stability of the electrode is reduced.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a vanadium-based glass negative electrode material, a preparation method and an application thereof, and a lithium ion battery prepared from the vanadium-based glass negative electrode material provided by the present invention has excellent electrochemical performance.
The invention provides a vanadium-based glass negative electrode material which is prepared from metal oxide, vanadium pentoxide and boron oxide;
the metal oxide is selected from Fe2O3、Ga2O3、Ln2O3、MgO、ZnO、CoO、NiO、CdO、Nb2O5And Y2O3At least one of;
the mass ratio of the metal oxide to the vanadium pentoxide to the boron oxide is 10-50: 40-70: 10 to 40.
The invention also provides a preparation method of the vanadium-based glass anode material, which comprises the following steps:
A) uniformly mixing metal oxide, vanadium pentoxide and boron oxide to obtain a mixed material;
B) melting the mixed material at 1000-2000 ℃ to obtain glass liquid;
C) cooling and forming the molten glass to obtain a glass sheet;
D) and crushing the glass slices, and performing ball milling to obtain the vanadium-based glass cathode material.
Preferably, in the step A), the particle size of the mixed material is not less than 400 meshes.
Preferably, in the step B), before melting the mixture at 1000 to 2000 ℃, the method further comprises:
and heating the mixed material to 1000-2000 ℃ at a speed of 5-15 ℃/min.
Preferably, in the step B), the melting time is 15-60 min.
The invention also provides a lithium ion battery negative plate which is prepared by uniformly mixing the raw materials including the negative material, the conductive material, the binder and the solvent and coating the mixture on the copper foil;
the negative electrode material is the vanadium-based glass negative electrode material or the vanadium-based glass negative electrode material prepared by the preparation method.
Preferably, the conductive material is acetylene black;
the binder is polyvinylidene fluoride or polytetrafluoroethylene;
the solvent is N-methyl pyrrolidone.
Preferably, the mass ratio of the negative electrode material to the conductive material to the binder is 6-10: 1-3: 1 to 2.
The invention also provides a lithium ion battery which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is the lithium ion battery negative plate.
The invention provides a vanadium-based glass negative electrode material which is prepared from metal oxide, vanadium pentoxide and boron oxide; the metal oxide is selected from Fe2O3、Ga2O3、Ln2O3、MgO、ZnO、CoO、NiO、CdO、Nb2O5And Y2O3At least one of; the mass ratio of the metal oxide to the vanadium pentoxide to the boron oxide is 10-50: 40-70: 10 to 40.
According to the invention, the vanadium-based glass negative electrode material is prepared by mixing the metal oxide, the vanadium pentoxide and the boron oxide with specific components according to a certain proportion, and the vanadium-based glass negative electrode material has the advantages of less capacity attenuation in a crystalline state, higher conductivity and better electrochemical performance. The vanadium-based glass negative electrode material is prepared into the lithium ion battery, and the obtained lithium ion battery has higher specific discharge capacity for the first time and better cycle performance.
Drawings
FIG. 1 is an XRD pattern of a vanadium-based glass anode material obtained in example 2 of the present invention;
FIG. 2 is a TEM image of the vanadium-based glass anode material obtained in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a vanadium-based glass negative electrode material which is prepared from metal oxide, vanadium pentoxide and boron oxide;
the metal oxide is selected from Fe2O3、Ga2O3、Ln2O3、MgO、ZnO、CoO、NiO、CdO、Nb2O5And Y2O3At least one of;
the mass ratio of the metal oxide to the vanadium pentoxide to the boron oxide is 10-50: 40-70: 10 to 40. In certain embodiments of the present invention, the mass ratio of the metal oxide, vanadium pentoxide, and boron oxide is 30: 50: 20. 30: 55: 15. 35: 45: 20. 40: 40: 20 or 30: 45: 25.
the invention also provides a preparation method of the vanadium-based glass anode material, which comprises the following steps:
A) uniformly mixing metal oxide, vanadium pentoxide and boron oxide to obtain a mixed material;
B) melting the mixed material at 1000-2000 ℃ to obtain glass liquid;
C) cooling and forming the molten glass to obtain a glass sheet;
D) and crushing the glass slices, and performing ball milling to obtain the vanadium-based glass cathode material.
In the preparation method of the vanadium-based glass cathode material provided by the invention, the adopted raw material components and the proportion are the same as above, and are not described again.
In step A):
in certain embodiments of the invention, the blending is stirred blending.
In certain embodiments of the invention, the particle size of the mixed material is not less than 400 mesh. In the invention, the particle size of the mixed material can be realized by sieving with a 400-mesh sieve.
In step B):
in some embodiments of the present invention, before melting the mixture at 1000-2000 ℃, the method further comprises:
in some embodiments of the invention, the temperature of the mixed material is raised to 1000-2000 ℃ at a rate of 5-15 ℃/min. In certain embodiments, the rate of temperature increase is 10 ℃/min.
In certain embodiments, the temperature of the melting is 1500 ℃.
In some embodiments of the present invention, the melting time is 15-60 min. In certain embodiments, the time for the melting is 40 min.
In step C):
in certain embodiments of the invention, step C) comprises:
and pouring the molten glass on a brass plate, extruding the molten glass by using the other brass plate, and forming to obtain the glass sheet.
In step D):
in certain embodiments of the invention, the method of disruption is trituration.
In certain embodiments of the invention, the ball milling is performed using a ball mill. The method of ball milling is not particularly limited in the present invention, and a ball milling method known to those skilled in the art may be used.
In some embodiments of the invention, the particle size of the vanadium-based glass anode material is 2-4 μm.
The vanadium-based glass cathode material prepared by the invention is an amorphous material.
The invention also provides a lithium ion battery negative plate which is prepared by uniformly mixing the raw materials including the negative material, the conductive material, the binder and the solvent and coating the mixture on the copper foil.
In the invention, the negative electrode material is the vanadium-based glass negative electrode material or the vanadium-based glass negative electrode material prepared by the preparation method.
In certain embodiments of the present invention, the conductive material is acetylene black.
In certain embodiments of the invention, the binder is polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE).
In certain embodiments of the present invention, the solvent is N-methylpyrrolidone.
In some embodiments of the invention, the mass ratio of the negative electrode material, the conductive material and the binder is 6-10: 1-3: 1-2, preferably 5-9: 2: 1. in certain embodiments, the mass ratio of the negative electrode material, the conductive material, and the binder is 8: 2: 1.
in some embodiments of the present invention, the lithium ion battery negative electrode sheet is prepared according to the following method:
a) grinding the negative electrode material, the conductive material and the binder to obtain mixed powder;
b) and stirring and mixing the mixed powder and a solvent to obtain slurry, uniformly coating the slurry on a copper foil, and drying to obtain the lithium ion battery negative plate.
In step a):
in certain embodiments of the invention, the particle size of the powder blend does not exceed 4 μm.
In step b):
in some embodiments of the invention, the stirring is magnetic stirring, and the stirring time is 24-30 hours. In certain embodiments, the stirring time is 26 hours.
The method and parameters for drying are not particularly limited in the present invention, and those known to those skilled in the art can be used.
The invention also provides a lithium ion battery which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is the lithium ion battery negative plate.
The selection of the anode, the separator and the electrolyte is not particularly limited in the present invention, and the anode, the separator and the electrolyte of the lithium ion battery well known to those skilled in the art can be used. The method for assembling the lithium ion battery is not particularly limited, and the lithium ion battery can be assembled by adopting an assembling method known by a person skilled in the art.
In order to research the performance of the vanadium-based glass negative electrode material, the lithium ion battery negative electrode piece is adopted, a metal lithium piece is taken as a counter electrode, Celgard 2025 is taken as a diaphragm, and 1mol/L LiPF6The solution is electrolyte, and the LiPF is6In the solution, the solvent comprises a solvent in a volume ratio of 1: 1 ethylene carbonate and dimethyl carbonate, to produce experimental cells. The method for assembling the experimental battery is not particularly limited, and the experimental battery can be assembled by a battery assembling method known to those skilled in the art.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
In order to further illustrate the present invention, the following detailed description of a vanadium-based glass negative electrode material, a preparation method and applications thereof are provided in connection with examples, which should not be construed as limiting the scope of the present invention.
Examples 1 to 5
Preparing a vanadium-based glass negative electrode material:
1) stirring and uniformly mixing the preparation raw materials, and sieving the mixture with a 400-mesh sieve for multiple times to obtain a mixed material; the preparation raw materials are shown in table 1;
2) putting the mixed material into a quartz boat, heating to 1500 ℃ at a speed of 10 ℃/min, and melting for 40min at 1500 ℃ to obtain glass liquid;
3) pouring the molten glass on a brass plate, extruding the molten glass by using the other brass plate, and forming to obtain a glass sheet;
4) and smashing the glass slices, and then ball-milling by using a ball mill to obtain the vanadium-based glass negative electrode material with the particle size of 2-4 microns.
TABLE 1 raw material components and parts by weight of examples 1 to 5
FIG. 1 is an XRD pattern of a vanadium-based glass anode material obtained in example 2 of the present invention. Fig. 1 shows a broad hump characteristic without sharp or discrete peaks, indicating that the resulting sample is an amorphous material.
FIG. 2 is a TEM image of the vanadium-based glass anode material obtained in example 3 of the present invention. Fig. 2 shows no lattice diffraction, indicating that the resulting sample is completely amorphous.
Examples 6 to 10
The lithium ion battery negative plate is prepared according to the following method:
a) grinding the vanadium-based glass negative electrode material prepared in the embodiment 1, acetylene black and polyvinylidene fluoride to obtain mixed powder; the particle size of the mixed powder is not more than 4 mu m;
b) and magnetically stirring and mixing the mixed powder and a solvent for 26h to obtain slurry, uniformly coating the slurry on a copper foil, and drying to obtain the lithium ion battery negative plate.
In examples 2 to 5, the above operations were repeated to prepare negative electrode sheets of lithium ion batteries.
Assembling the experimental battery:
the lithium ion battery negative plate is adopted, a metal lithium plate is taken as a counter electrode, Celgard 2025 is taken as a diaphragm, and 1mol/L LiPF6The solution is electrolyte, and the LiPF is6In the solution, the solvent comprises a solvent in a volume ratio of 1: 1 ethylene carbonate and dimethyl carbonate, assembled into CR2016 type coin cells in a glove box.
When the negative electrode sheet was the negative electrode sheet for lithium ion batteries of examples 6, 7, 8, 9, and 10, the CR2016 type coin cells produced were designated as battery 1, battery 2, battery 3, battery 4, and battery 5, respectively.
The electrochemical performance of each battery is tested by adopting a test instrument LANHE CT3001A blue battery test system under the test condition of room temperature and under the conditions of 0.1C and 0.01-3V of charge-discharge voltage, and is shown in table 2.
TABLE 2 electrochemical Performance test results for batteries 1-5
The preparation method is simple, and the prepared electrode material has high specific capacity, good cycling stability in the charging and discharging processes and high capacity retention rate in the long cycling process.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A vanadium-based glass negative electrode material is prepared from metal oxide, vanadium pentoxide and boron oxide;
the metal oxide is selected from Fe2O3、Ga2O3、Ln2O3、MgO、ZnO、CoO、NiO、CdO、Nb2O5And Y2O3At least one of;
the mass ratio of the metal oxide to the vanadium pentoxide to the boron oxide is 10-50: 40-70: 10 to 40.
2. The method of preparing the vanadium-based glass anode material of claim 1, comprising the steps of:
A) uniformly mixing metal oxide, vanadium pentoxide and boron oxide to obtain a mixed material;
B) melting the mixed material at 1000-2000 ℃ to obtain glass liquid;
C) cooling and forming the molten glass to obtain a glass sheet;
D) and crushing the glass slices, and performing ball milling to obtain the vanadium-based glass cathode material.
3. The method according to claim 2, wherein the particle size of the mixed material in step a) is not less than 400 mesh.
4. The preparation method according to claim 2, wherein before melting the mixture at 1000 to 2000 ℃ in step B), the method further comprises:
and heating the mixed material to 1000-2000 ℃ at a speed of 5-15 ℃/min.
5. The method according to claim 2, wherein the melting time in step B) is 15 to 60 min.
6. A lithium ion battery negative plate is prepared by uniformly mixing raw materials including a negative material, a conductive material, a binder and a solvent, and coating the mixture on a copper foil;
the negative electrode material is the vanadium-based glass negative electrode material in claim 1 or the vanadium-based glass negative electrode material prepared by the preparation method in any one of claims 2 to 5.
7. The lithium ion battery negative electrode sheet according to claim 6, wherein the conductive material is acetylene black;
the binder is polyvinylidene fluoride or polytetrafluoroethylene;
the solvent is N-methyl pyrrolidone.
8. The lithium ion battery negative electrode sheet according to claim 6, wherein the mass ratio of the negative electrode material to the conductive material to the binder is 6-10: 1-3: 1 to 2.
9. A lithium ion battery is characterized by comprising a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode is the lithium ion battery negative electrode piece of any one of claims 6 to 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02165565A (en) * | 1988-12-16 | 1990-06-26 | Otsuka Chem Co Ltd | Full solid secondary cell |
| US6132903A (en) * | 1997-07-17 | 2000-10-17 | Sanyo Electric Co., Ltd. | Lithium secondary battery comprising a negative electrode consisting essentially of B2 O3 |
| CN104821392A (en) * | 2015-05-06 | 2015-08-05 | 中南大学 | Preparation method of spherical lithium ion battery anode material vanadium borate |
| KR20180090479A (en) * | 2017-02-03 | 2018-08-13 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery comprising Vanadium oxide coated with Boron trioxide and manufacturing method thereof |
| CN112838204A (en) * | 2021-01-07 | 2021-05-25 | 欣旺达电动汽车电池有限公司 | Negative electrode active material, preparation method thereof, negative electrode material, negative electrode sheet and battery |
-
2021
- 2021-12-28 CN CN202111628611.7A patent/CN114300670B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02165565A (en) * | 1988-12-16 | 1990-06-26 | Otsuka Chem Co Ltd | Full solid secondary cell |
| US6132903A (en) * | 1997-07-17 | 2000-10-17 | Sanyo Electric Co., Ltd. | Lithium secondary battery comprising a negative electrode consisting essentially of B2 O3 |
| CN104821392A (en) * | 2015-05-06 | 2015-08-05 | 中南大学 | Preparation method of spherical lithium ion battery anode material vanadium borate |
| KR20180090479A (en) * | 2017-02-03 | 2018-08-13 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery comprising Vanadium oxide coated with Boron trioxide and manufacturing method thereof |
| CN112838204A (en) * | 2021-01-07 | 2021-05-25 | 欣旺达电动汽车电池有限公司 | Negative electrode active material, preparation method thereof, negative electrode material, negative electrode sheet and battery |
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