CN115784247A - Low-voltage cathode material of lithium ion battery and preparation method and application thereof - Google Patents
Low-voltage cathode material of lithium ion battery and preparation method and application thereof Download PDFInfo
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- CN115784247A CN115784247A CN202211590738.9A CN202211590738A CN115784247A CN 115784247 A CN115784247 A CN 115784247A CN 202211590738 A CN202211590738 A CN 202211590738A CN 115784247 A CN115784247 A CN 115784247A
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- lithium
- lithium ion
- ion battery
- negative electrode
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010406 cathode material Substances 0.000 title abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims abstract description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 5
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims abstract description 5
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a low-voltage cathode material of a lithium ion battery, a preparation method and application thereof, in particular to Li 2 VSiO 5 A low-voltage cathode material of a lithium ion battery and a preparation method and application thereof belong to the technical field of lithium ion battery materials. The preparation method of the low-voltage negative electrode material of the lithium ion battery comprises the following steps: a. mixing a lithium source, silicon dioxide and a vanadium source according to a molar ratio of 1-2, wherein the particle size of the silicon dioxide is 10-20 nm, the particle size of the vanadium source is less than 50nm, the lithium source is at least one of lithium nitrate, lithium carbonate or lithium hydroxide, and the vanadium source is one of vanadium dioxide, vanadium trioxide or vanadium pentoxide to obtain a mixture; b. and sintering the mixture in an inert protective atmosphere at the temperature of 850-900 ℃ for 8-11 h. The invention has simple processHas low requirement on equipment and low preparation cost, and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to a low-voltage cathode material of a lithium ion battery, a preparation method and application thereof, in particular to Li 2 VSiO 5 A low-voltage cathode material of a lithium ion battery and a preparation method and application thereof belong to the technical field of lithium ion battery materials.
Background
The rapid increase in energy demand has driven the application and development of new energy storage systems, and advanced secondary battery related industries have become a leading future emerging field. The lithium ion battery as the most representative battery system has the advantages of high capacity, good cycle stability and the like, and is widely applied to the fields of electronic devices and automobiles. The energy density of a lithium ion battery is mainly determined by the specific capacity (i.e., the capacity of storing electricity per unit weight/volume of the material) and the operating voltage of the electrode material. The development of negative electrode materials with high specific capacity and low voltage and the great improvement of the service life of the negative electrode materials become the key and difficult point of the research of the lithium ion battery.
The electrode material is an important component of the lithium ion battery, and the performance of the electrode material is closely related to the energy density, the cycle life and the safety of the battery. The search for suitable anode materials is key to improving the performance of lithium ion batteries. To date, most commercial lithium ion batteries employ intercalation-based negative electrode materials. Wherein the reversible theoretical capacity of the graphite is 372mAh g -1 However, compared to Li +/Li, an operating potential below 0.1V will result in the formation of lithium dendrites and present a series of safety issues. Lithium titanate (Li) 4 Ti 5 O 12 ) Has a high working voltage of 1.55V, but a lower capacity of 175mAh g -1 It remains a major problem. The silicon has abundant reserves, environment-friendly, proper lithiation voltage platform and ultrahigh theoretical capacity (4200 mAh g) -1 ) Etc., but there is a large volume expansion (Si) during charge-discharge cycles>300%), and high cost, which seriously hinders its wide application.
In addition, the power of the battery is in direct proportion to the voltage of the battery, the voltage of the single battery is mainly determined by the potential difference between the anode material and the cathode material, namely the voltage of the single battery is the voltage of the anode minus the voltage of the cathode, and the lower the voltage of the cathode is, the more beneficial to improving the power of the single battery is, and the development of the cathode material with low voltage has important significance for improving the power of the battery. Therefore, it is necessary to accelerate the development of a novel low-voltage negative electrode material.
CN111211325A discloses a lithium ion battery cathode material and a preparation method and application thereof. The invention discloses a preparation method of a lithium ion battery cathode material with a chemical formula of Li 2 VSi (1-x) Ge (x) O 5 (ii) a Wherein x is more than or equal to 0 and less than or equal to 1. The negative electrode material has moderate discharge platform and higher capacity, the initial discharge specific capacity of the negative electrode material is about 1300mAh/g after the half-cell is assembled, the volume expansion in the charge-discharge process is small, the conductivity is good, and the negative electrode material has better cycle performance and rate capability, solves the problems of poorer electrochemical performance, specific capacity, cycle performance and rate capability of the oxide negative electrode material, but has high negative electrode voltage and about 1V average working potential. In addition, in CN111211325A, the raw materials are weighed according to the stoichiometric ratio and dispersed in an organic solvent at 60-70 ℃ for 6-20 hours to obtain gel, and the preferable scheme is that the gel is ball milled at the rotating speed of 900 r/min for 5 hours, calcined at 800 ℃ for 12 hours and then calcined at 925 ℃ for 12 hours to finally obtain the cathode material Li 2 VSi (1-x) Ge (x) O 5 . The steps are complicated, the energy consumption and the time (>30 hours) was very high.
Disclosure of Invention
The invention aims to provide a preparation method of a low-voltage negative electrode material of a lithium ion battery.
In order to achieve the first object of the present invention, the method for preparing the low-voltage negative electrode material of the lithium ion battery comprises:
a. mixing a lithium source, silicon dioxide and a vanadium source according to a molar ratio of 1-2, wherein the particle size of the silicon dioxide is 10-20 nm, the particle size of the vanadium source is less than 50nm, the lithium source is at least one of lithium nitrate, lithium carbonate or lithium hydroxide, and the vanadium source is one of vanadium dioxide, vanadium trioxide or vanadium pentoxide to obtain a mixture;
b. and sintering the mixture in an inert protective atmosphere at the temperature of 850-900 ℃ for 8-11 h.
In one embodiment, the inert protective atmosphere is at least one of nitrogen or argon.
In one embodiment, the lithium source, silica, vanadium source are present in a molar ratio of 1.
The second purpose of the invention is to provide a novel low-voltage negative electrode material of a lithium ion battery.
In order to achieve the second object of the present invention, the material is prepared by the method for preparing the low voltage negative electrode material of the lithium ion battery.
In one embodiment, the low voltage negative electrode material of the lithium ion battery has a discharge voltage of 0.5V or less.
In one embodiment, the low voltage negative electrode material of the lithium ion battery has a discharge voltage of 0.25V or less.
The third purpose of the invention is to provide the application of the low-voltage negative electrode material of the lithium ion battery as a negative electrode material in the preparation of the lithium ion battery.
Has the advantages that:
the voltage of the cathode material is as low as 0.5V or less, which is beneficial to improving the voltage and power of the battery.
The invention provides a novel Li 2 VSiO 5 A low-voltage cathode material of a lithium ion battery, a preparation method and application thereof. The preparation method has the advantages of simple preparation process, low requirement on equipment and low preparation cost, and is suitable for industrial large-scale production.
Detailed Description
In order to achieve the first object of the present invention, the method for preparing the low-voltage negative electrode material of the lithium ion battery comprises:
a. mixing a lithium source, silicon dioxide and a vanadium source according to a molar ratio of 1-2, wherein the particle size of the silicon dioxide is 10-20 nm, the particle size of the vanadium source is less than 50nm, the lithium source is at least one of lithium nitrate, lithium carbonate or lithium hydroxide, and the vanadium source is one of vanadium dioxide, vanadium trioxide or vanadium pentoxide to obtain a mixture;
b. and sintering the mixture in an inert protective atmosphere at the temperature of 850-900 ℃ for 8-11 h.
In one embodiment, the inert protective atmosphere is at least one of nitrogen or argon.
In one embodiment, the lithium source, silica, vanadium source are present in a molar ratio of 1.
In order to achieve the second object of the present invention, the material is prepared by the method for preparing the low voltage negative electrode material of the lithium ion battery.
In one embodiment, the low voltage negative electrode material of the lithium ion battery has a discharge voltage of 0.5V or less.
In one embodiment, the low voltage negative electrode material of the lithium ion battery has a discharge voltage of 0.25V or less.
The invention also provides a use of the low-voltage negative electrode material of the lithium ion battery as a negative electrode material in the preparation of the lithium ion battery.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Weighing 0.01mol of lithium carbonate, 0.01mol of silicon dioxide with the granularity of 15-20 nm and 0.011mol of vanadium dioxide with the granularity of 20-30 nm, uniformly mixing the three kinds of powder, putting the powder into a tubular furnace for solid-phase sintering, introducing nitrogen protective gas, heating to 870 ℃, keeping the temperature at constant temperature for 10 hours, and then cooling along with the furnace; to obtain Li 2 VSiO 5 A low-voltage cathode material of a lithium ion battery. Measurement of the obtained Li 2 VSiO 5 The lithium ion battery performance results of the low voltage negative electrode material of the lithium ion battery are shown in table 1.
Example 2
Weighing 0.02mol of lithium nitrate, 0.01mol of silicon dioxide with the granularity of 10-15 nm and 0.006mol of vanadium pentoxide with the granularity of 20-30 nm, uniformly mixing the three powders and placing the mixturePutting the mixture into a tube furnace for solid-phase combustion, introducing nitrogen protective gas, heating to 850 ℃, keeping the temperature for 12 hours at constant temperature, and then cooling along with the furnace; to obtain Li 2 VSiO 5 A low-voltage cathode material of a lithium ion battery. Measurement of the obtained Li 2 VSiO 5 The lithium ion battery performance of the low voltage negative electrode material of the lithium ion battery is shown in table 1.
Example 3
Weighing 0.01mol of lithium nitrate, 0.01mol of silicon dioxide with the granularity of 10-15 nm and 0.006mol of vanadium pentoxide with the granularity of 20-30 nm, uniformly mixing the three kinds of powder, putting the powder into a tubular furnace, solidifying and sintering the mixture, introducing argon protective gas, heating to 950 ℃, keeping the temperature at constant temperature for 8 hours, and then cooling the mixture along with the furnace; to obtain Li 2 VSiO 5 A low-voltage cathode material of a lithium ion battery. Measurement of the obtained Li 2 VSiO 5 The lithium ion battery performance of the low voltage negative electrode material of the lithium ion battery is shown in table 1.
TABLE 1 Li of the invention 2 VSiO 5 Lithium ion battery low voltage cathode material performance test result
| Sample name | Physical phase | Discharge voltage (V) | First discharge capacity mAh/g |
| Example 1 | Li 2 VSiO 5 | 0.25 | 627 |
| Example 2 | Li 2 VSiO 5 | 0.25 | 623 |
| Example 3 | Li 2 VSiO 5 | 0.25 | 625 |
As can be seen from Table 1, li of the present invention 2 VSiO 5 The discharge voltage of the low-voltage cathode material of the lithium ion battery is lower than 0.5V, and the low-voltage cathode material has high discharge capacity.
Claims (7)
1. The preparation method of the low-voltage negative electrode material of the lithium ion battery is characterized by comprising the following steps of:
a. mixing a lithium source, silicon dioxide and a vanadium source according to a molar ratio of 1-2, wherein the particle size of the silicon dioxide is 10-20 nm, the particle size of the vanadium source is less than 50nm, the lithium source is at least one of lithium nitrate, lithium carbonate or lithium hydroxide, and the vanadium source is one of vanadium dioxide, vanadium trioxide or vanadium pentoxide to obtain a mixture;
b. and sintering the mixture in an inert protective atmosphere at the temperature of 850-900 ℃ for 9-11 h.
2. The method for preparing a low-voltage negative electrode material of a lithium ion battery according to claim 1, wherein the inert protective atmosphere is at least one of nitrogen or argon.
3. The preparation method of the low-voltage negative electrode material of the lithium ion battery, according to claim 1 or 2, is characterized in that the molar ratio of the lithium source, the silicon dioxide and the vanadium source is 1.
4. The low-voltage negative electrode material of the lithium ion battery is characterized by being prepared by the preparation method of the low-voltage negative electrode material of the lithium ion battery according to any one of claims 1 to 3.
5. The low-voltage negative electrode material for lithium ion batteries according to claim 4, wherein the discharge voltage of the low-voltage negative electrode material for lithium ion batteries is 0.5V or less.
6. The low-voltage negative electrode material for lithium-ion batteries according to claim 5, wherein the discharge voltage of said low-voltage negative electrode material for lithium-ion batteries is 0.25V or less.
7. Use of the low voltage negative electrode material of a lithium ion battery according to any of claims 4 to 6 as a negative electrode material in the preparation of a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211590738.9A CN115784247A (en) | 2022-12-12 | 2022-12-12 | Low-voltage cathode material of lithium ion battery and preparation method and application thereof |
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|---|---|---|---|
| CN202211590738.9A CN115784247A (en) | 2022-12-12 | 2022-12-12 | Low-voltage cathode material of lithium ion battery and preparation method and application thereof |
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| CN115784247A true CN115784247A (en) | 2023-03-14 |
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| CN202211590738.9A Pending CN115784247A (en) | 2022-12-12 | 2022-12-12 | Low-voltage cathode material of lithium ion battery and preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111211325A (en) * | 2020-03-09 | 2020-05-29 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
| CN113437291A (en) * | 2021-07-27 | 2021-09-24 | 西安交通大学 | Lithium vanadium fluorophosphosilicate cathode material and preparation method thereof |
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2022
- 2022-12-12 CN CN202211590738.9A patent/CN115784247A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111211325A (en) * | 2020-03-09 | 2020-05-29 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
| CN113437291A (en) * | 2021-07-27 | 2021-09-24 | 西安交通大学 | Lithium vanadium fluorophosphosilicate cathode material and preparation method thereof |
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