CN107565119B - Negative electrode active material, preparation method thereof and lithium ion battery - Google Patents
Negative electrode active material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN107565119B CN107565119B CN201610498757.7A CN201610498757A CN107565119B CN 107565119 B CN107565119 B CN 107565119B CN 201610498757 A CN201610498757 A CN 201610498757A CN 107565119 B CN107565119 B CN 107565119B
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Abstract
The invention relates to a rod-shaped lithium molybdate cathode active material, wherein the rod-shaped lithium molybdate is of a micron-sized rod-shaped structure; the diameter of the rod-shaped lithium molybdate is 1-2 mu m; the length is 1-7 μm. The invention also provides a preparation method of the rod-shaped lithium molybdate cathode active material and a lithium ion battery. According to the invention, the micron-sized rod-shaped lithium molybdate is used as the negative active material, the particle size is smaller, the de-intercalation of lithium ions is facilitated, meanwhile, the solid structure is beneficial to reducing the specific surface area of the material, reducing side reactions and improving the compaction density and the volume specific capacity of the material, and the preparation process is simple.
Description
Technical Field
The invention relates to a negative electrode active material, a preparation method thereof and a lithium ion battery.
Background
The application field of the lithium ion battery has been rapidly expanded from the first mobile communication to various aspects including various portable electronic products, relating to life and entertainment, military, aerospace, medical treatment and communication of people, and is developing to large and medium-sized energy storage devices, power sources and the like after the lithium ion battery has been born for less than 20 years now. The great commercial success of lithium ion batteries and the promotion of the development in the above field are incomparable with any secondary battery.
The prior art (201310237337. X) discloses a preparation method of a lithium molybdate cathode material of a lithium ion battery, which comprises the steps of uniformly mixing lithium salt and molybdenum salt precursors according to a stoichiometric ratio (molar ratio), heating the mixture in air to 200-800 ℃ for heat preservation pretreatment, and then carrying out sintering reaction in air or inert atmosphere of nitrogen, argon and carbon dioxide at the temperature of 500-800 ℃ to obtain lithium molybdate (Li-237337. X) of the lithium ion battery2MoO4) And (3) a negative electrode material. However, the lithium molybdate anode material prepared by the high-temperature solid-phase method has many defects, the raw materials are difficult to achieve uniform mixing on an atomic level, the particle size of the product is large due to high-temperature sintering, the lithium molybdate anode material is not beneficial to the de-intercalation of lithium ions, and the influence on the performance of the lithium molybdate anode material is large.
Prior art (2013)10237338.4) discloses another sol-gel preparation method of lithium molybdate negative electrode of lithium ion battery, MoO is added3Dissolving the powder in distilled water, placing on a magnetic stirrer, stirring, heating to 80 deg.C to obtain gray suspension, adding lithium salt to obtain uniform and stable colloid, and vacuum drying to obtain lithium molybdate (Li)2MoO4) And (3) a negative electrode material. The obtained material has a tubular shape with the length of about 5 mu m, has small particle size and is beneficial to improving the electrochemical performance of the material. However, the tubular shape causes large specific surface area and low compaction density, thereby causing more side reactions and lower volume specific capacity.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the lithium molybdate electrode material has larger particle size and larger specific surface area, is not beneficial to the de-intercalation of lithium ions, and has lower compaction density, so that more side reactions and lower volume specific capacity are caused. In particular to a micron-sized rod-shaped negative active material with small particle size, which is beneficial to the deintercalation of lithium ions, is beneficial to reducing the specific surface area of the material, reducing side reactions, improving the compacted density and the volume specific capacity of the material, and has simple preparation process, a preparation method thereof and a lithium ion battery.
In order to solve the above problems, the present invention provides a rod-shaped lithium molybdate negative active material, wherein the rod-shaped lithium molybdate has a micron-sized rod-shaped structure; the diameter of the rod-shaped lithium molybdate is 1-2 mu m; the length is 1-7 μm.
The invention also provides a preparation method of the rod-shaped lithium molybdate anode active material, which comprises the following steps:
s1, mixing lithium molybdate with the mixed solution of water and polyhydric alcohol;
and S2, heating, cooling and separating to obtain the rod-shaped lithium molybdate negative electrode active material.
A lithium ion battery comprises a shell, and an electric core and an electrolyte which are accommodated in the shell, wherein the electric core comprises a positive electrode, a negative electrode and a diaphragm which is arranged between the positive electrode and the negative electrode; the negative electrode comprises a negative electrode current collector and a negative electrode material; the negative electrode material includes a negative electrode active material, wherein the negative electrode active material is the negative electrode active material described above.
According to the invention, the rod-shaped lithium molybdate is used as the negative electrode active material, and the rod-shaped lithium molybdate is small in particle size, so that the de-intercalation of lithium ions is facilitated, the specific surface area of the material is reduced, the side reaction is reduced, and the compaction density and the volume specific capacity of the material are improved. Dissolving lithium molybdate in a mixed solution of water and polyhydric alcohol, wherein the lithium molybdate is dissolved in the water and is not dissolved in the polyhydric alcohol, and the polyhydric alcohol can inhibit Li2MoO4The growth of the crystal grains simultaneously plays the role of structure orientation and a dispersing agent. On one hand, hydroxyl in the polyhydric alcohol adsorbs metal ions, so that the metal ions are linearly arranged, and the sheet-shaped and rod-shaped appearances are favorably formed. On the other hand, the polyol can uniformly disperse the raw materials in the mixed solution of the polyol and the water, the water content of the mixed solution is lower and lower along with the increase of the temperature, and when the mixed solution reaches a supersaturated state, the Li can be caused by continuously increasing the temperature2MoO4There was precipitation at each position and no large particles were present. Finally, the separated clear liquid has low water content, is mainly polyhydric alcohol, can be recycled and continuously used, and cannot cause waste.
Drawings
Fig. 1 is a scanning electron micrograph of a rod-shaped lithium molybdate negative active material S1 obtained in example 1 of the present invention;
fig. 2 is a charge-discharge curve of the battery S10 of the present invention;
fig. 3 is a cycle life curve for batteries S10 and DS20 of the present invention.
Detailed Description
The invention provides a rod-shaped lithium molybdate cathode active material, wherein the rod-shaped lithium molybdate is of a micron-sized rod-shaped structure; the diameter of the rod-shaped lithium molybdate is 1-2 mu m; the length is 1-7 μm. The rod-shaped lithium molybdate is small in particle size and beneficial to the de-intercalation of lithium ions, and meanwhile, the solid structure is beneficial to reducing the specific surface area of the material, reducing side reactions and improving the compaction density and the volume specific capacity of the material. The material with the diameter less than 100nm has large specific surface area, and can generate more side reactions when used as an electrode material; materials having a particle size of more than 10 μm are not favorable for the deintercalation of lithium ions, and are not suitable as electrode materials.
The invention also provides a preparation method of the rod-shaped lithium molybdate cathode active material, which comprises the following steps:
s1, mixing lithium molybdate with the mixed solution of water and polyhydric alcohol;
and S2, heating, cooling and separating to obtain the rod-shaped lithium molybdate negative electrode active material.
Dissolving lithium molybdate in a mixed solution of water and polyhydric alcohol, wherein the lithium molybdate is dissolved in the water and is not dissolved in the polyhydric alcohol, and the polyhydric alcohol can inhibit Li2MoO4The growth of the crystal grains simultaneously plays the role of structure orientation and a dispersing agent. On one hand, hydroxyl in the polyhydric alcohol adsorbs metal ions, so that the metal ions are linearly arranged, and the sheet-shaped and rod-shaped appearances are favorably formed. On the other hand, the polyol can uniformly disperse the raw materials in the mixed solution of the polyol and the water, the water content of the mixed solution is lower and lower along with the increase of the temperature, and when the mixed solution reaches a supersaturated state, the Li can be caused by continuously increasing the temperature2MoO4There was precipitation at each position and no large particles were present. The separated clear liquid has low water content, is mainly polyhydric alcohol, can be recycled and continuously used, and cannot cause waste. The technical problems of the lithium molybdate anode material prepared by the high-temperature solid-phase method are solved: the raw materials are difficult to achieve uniform mixing on an atomic level, the particle size of a product is large due to high-temperature sintering, the desorption of lithium ions is not facilitated, and the influence on the performance of the lithium molybdate anode material is large.
Preferably, the lithium molybdate is non-rod-shaped lithium molybdate with the particle size of more than 10 μm, and can be purchased or synthesized by self.
Preferably, the amount of the lithium molybdate is 0.5 to 3 parts by weight with respect to 100 parts by weight of the polyol. Further preferably, the amount of lithium molybdate added is 1 to 2 parts by weight. When the added lithium molybdate is excessive, more lithium molybdate is simultaneously precipitated in the solvent with the same volume, and the product with larger diameter is easy to grow.
Preferably, the mass ratio of water to the polyhydric alcohol in the water-polyhydric alcohol mixed solution is 1:20 to 50. The water in the mixed solvent is a carrier of lithium molybdate, the solubility of the lithium molybdate is higher, the requirement can be met by less water, and for the same mass of lithium molybdate, the larger the volume of the dispersant polyalcohol is, the smaller the particle size of the obtained rod-shaped lithium molybdate is.
Preferably, the heating temperature is 180-250 ℃, and the heating time is 1-2 h. Further preferably, the heating temperature is 190-200 ℃, and the heating time is 1-2 h.
Preferably, the mixing method can be magnetic stirring and other techniques commonly used in the art. The separation mode adopts the conventional use technology in the field, and centrifugal separation is selected in the application.
Preferably, the polyhydric alcohol is one or more selected from Ethylene Glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG) and tetraethylene glycol (TTEG).
The invention also provides a lithium ion battery, which comprises a shell, and an electric core and electrolyte which are accommodated in the shell, wherein the electric core comprises an anode, a cathode and a diaphragm between the anode and the cathode; the negative electrode comprises a negative electrode current collector and a negative electrode material; the negative electrode material comprises a negative electrode active material and a negative electrode binder, wherein the negative electrode active material is the negative electrode active material; the negative electrode material may also optionally include a conductive agent, which is a conventional conductive agent, and may be the same as or different from the conductive agent in the positive electrode material layer, and the negative electrode binder may be a negative electrode binder conventionally used in the art. The positive electrode comprises a positive electrode current collector and a positive electrode material, the positive electrode material comprises a positive electrode active material, a conductive agent and a positive electrode binder, and the conductive agent and the positive electrode binder can be conductive agents and positive electrode binders which are conventionally used in the field; the electrolyte is an electrolyte conventionally used in the field; the separator is a separator conventionally used in the art.
Since the preparation processes of the negative electrode plate, the electrolyte, the positive electrode plate and the separator are well known in the art, and the assembly of the battery is also well known in the art, the detailed description is omitted here.
The following will further describe the negative active material and the lithium ion battery containing the negative active material according to the present invention with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The raw materials used in the examples and comparative examples were obtained commercially.
Example 1
Weighing 2g of lithium molybdate, namely a high-temperature solid-phase sintering product of lithium molybdate, dissolving the lithium molybdate in a mixed solution of 6g of water and 200g of DEG, magnetically stirring, heating to 200 ℃, keeping the temperature for 1h, cooling to room temperature, carrying out centrifugal separation, and washing with ethanol to obtain a micron-sized rod-shaped lithium molybdate product, which is marked as S1. The scanning electron micrograph of the product S1 is shown in FIG. 1.
The diameter of the prepared S1 is 1.5 +/-0.3 mu m; the length was 5 μm.
Example 2
Weighing 4g of lithium molybdate, namely a high-temperature solid-phase sintering product of lithium molybdate, dissolving the lithium molybdate in a mixed solution of 8g of water and 200g of TEG, magnetically stirring, heating to 190 ℃, keeping the temperature for 2h, cooling to room temperature, carrying out centrifugal separation, and washing with ethanol to obtain a micron-sized rod-shaped lithium molybdate product, which is marked as S2.
The diameter of the prepared S2 is 1.7 +/-0.3 mu m; the length was 7 μm.
Example 3
Weighing 6g of lithium molybdate, namely a high-temperature solid-phase sintering product of lithium molybdate, dissolving the lithium molybdate in a mixed solution of 10g of water and 200gEG, magnetically stirring, heating to 180 ℃, keeping the temperature for 2h, cooling to room temperature, carrying out centrifugal separation, and washing with ethanol to obtain a micron-sized rod-shaped lithium molybdate product, which is marked as S3.
The diameter of the prepared S3 is 1.8 +/-0.3 mu m; the length was 8 μm.
Example 4
Weighing 1g of lithium molybdate high-temperature solid phase sintering product Li2MoO4, dissolving in a mixed solution of 4g of water and 200g of TTEG, magnetically stirring, heating to 200 ℃, keeping for 2h, cooling to room temperature, performing centrifugal separation, and cleaning with ethanol to obtain a micron-scale rod-shaped Li2MoO4 product, which is marked as S4.
The diameter of the prepared S4 is 1.3 +/-0.3 mu m; the length was 3 μm.
Example 5
Weighing 1g of lithium molybdate high-temperature solid phase sintering product Li2MoO4, dissolving in a mixed solution of 3g of water and 200g of TTEG, magnetically stirring, heating to 200 ℃ for 2h, cooling to room temperature, performing centrifugal separation, and cleaning with ethanol to obtain a micron-scale rod-shaped Li2MoO4 product, which is marked as S5.
The diameter of the prepared S5 is 1.0 +/-0.3 mu m; the length is 1 μm.
Comparative example 1
With reference to patent application No. 201310237338.4, a sol-gel process for the preparation of Li2MoO4The material, labeled DS 1.
The obtained DS1 has a tubular shape and a length of 5 μm.
Comparative example 2
With reference to the patent with application number 201310237337.X, Li is obtained by a high-temperature solid-phase preparation method2MoO4Material, labeled DS2
The obtained DS2 has no regular shape and the particle size is 10-30 μm.
Performance testing
1. Scanning electron microscope test
Testing an instrument: JSM-7600F type field emission scanning electron microscope
The test method comprises the following steps: performing a field emission electron microscope scanning test on the above example 1, and analyzing the microstructure of the negative active material S1 by magnifying the sample by 5000 times, thereby obtaining fig. 1; examples 2 to 5 and comparative examples 1 to 2 were measured according to the test method of test example 1.
And (3) testing results: the SEM photograph of the negative active material S1 prepared in example 1 shows that the product is rod-shaped particles having a diameter of about 1.5 μm and has good dispersibility.
2. Manufacturing the battery:
the positive plate of the test battery is prepared by uniformly mixing and tabletting electrode active materials (S1-S5) and acetylene black according to the mass ratio to PVDF = 85:10:5 respectively, and drying the plate in vacuum at 120 ℃ for more than 24 h. A metal lithium sheet is used as a negative electrode, a celgard2400 polypropylene porous membrane is used as a diaphragm, and a mixed solution (volume ratio =1:1) of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) of 1mol/L LiPF6 is used as an electrolyte. The assembly of all cells was carried out in a glove box filled with argon, resulting in cell samples S10-S50 in sequence.
Cell samples DS 10-DS 20 were prepared in the same manner as described above, except that: the electrode active material is DS 1-DS 2.
3. Electrochemical performance test
Testing equipment: a rechargeable battery performance measuring device BK-6808AR/2mA (Lanqi electronics industries, Ltd.).
The test method comprises the following steps: standing for 5min, inserting lithium at 0.1C, and cutting off voltage of 0.1V. After standing for 10min, the lithium is removed at 0.1C, and the lithium removal cut-off voltage is 2.5V. The charge/discharge rate during the cycle was set to 0.5C, and the cycle step was set to 50 cycles.
The test method is adopted to test the charge and discharge capacity, the charge and discharge capacity and the capacity retention rate of the battery samples S10-S50 and DS 10-DS 20 after 50 times of circulation, and the test results are shown in Table 1.
The mass specific capacity comprises mass ratio lithium intercalation capacity (discharge capacity) and mass ratio lithium deintercalation capacity (charge capacity), and the mass ratio lithium intercalation capacity and the mass ratio lithium deintercalation capacity are calculated according to the lithium intercalation capacity and the lithium deintercalation capacity and are the ratio of the actually measured lithium deintercalation capacity to the actually attached active material content of the pole piece. The capacity retention rate is a percentage of the discharge capacity after 50 cycles and the first discharge capacity.
Fig. 2 is a charge/discharge curve at a charge/discharge rate of 0.1C of a battery sample S10 produced in S1. It was found that the first discharge capacity of S10 was 1133.7mAh/g, the first charge capacity was 823.6mAh/g, and the second discharge capacity was 806.0 mAh/g. The test results for each cell are shown in table 1 below.
As can be seen from the test results in Table 1, the battery samples S10-S50 prepared by the preparation method provided by the invention have high charge and discharge capacity, which is obviously superior to the battery samples DS 10-DS 20 of the comparative examples.
Fig. 3 is a cycle life curve of a battery S10 made of S1 and a battery DS20 made of DS2, where the discharge capacity of the S10 battery after 50 cycles is 543.3mAh/g, the capacity retention rate is 47.9%, the discharge capacity of the DS20 battery after 50 cycles is 149.2mAh/g, and the capacity retention rate is 18.5%, which indicates that the micron-sized rod-shaped negative electrode active material provided by the present invention has a high discharge capacity and good charge-discharge cycle stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A method for preparing a rod-shaped lithium molybdate anode active material is characterized by comprising the following steps:
s1, mixing lithium molybdate with large particle size with a mixed solution of water and polyhydric alcohol, wherein the lithium molybdate with large particle size is non-rod-shaped lithium molybdate with particle size of more than 10 mu m;
s2, heating, cooling and separating to obtain a rod-shaped lithium molybdate negative electrode active material;
wherein the amount of the lithium molybdate is 0.5 to 3 parts by weight with respect to 100 parts by weight of the polyol in S1; the mass ratio of water to the polyhydric alcohol in the mixed solution of water and the polyhydric alcohol is 1: 20-50;
the heating temperature in S2 is 180-250 ℃, the heating time is 1-2 hours, and the rod-shaped lithium molybdate cathode active material in S2 is of a micron-sized rod-shaped structure; the diameter of the rod-shaped lithium molybdate is 1-2 mu m; the length is 1-7 μm.
2. The method of preparing a rod-shaped lithium molybdate anode active material according to claim 1, wherein the amount of the large-particle size lithium molybdate is 1 to 2 parts by weight with respect to 100 parts by weight of the polyol.
3. The method of preparing a rod-shaped lithium molybdate anode active material according to claim 1, wherein the polyol is one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol.
4. A lithium ion battery comprises a shell, and an electric core and an electrolyte which are accommodated in the shell, wherein the electric core comprises a positive electrode, a negative electrode and a diaphragm which is arranged between the positive electrode and the negative electrode; the negative electrode comprises a negative electrode current collector and a negative electrode material; the negative electrode material comprises a negative electrode active material, and is characterized in that the negative electrode active material is prepared by the preparation method of any one of claims 1 to 3.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241642A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Lithium molybdate cathode material for lithium ion battery and preparation method thereof |
| CN104229894A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Sol-gel method for preparation of lithium ion battery lithium molybdate cathode material |
| CN104577088A (en) * | 2013-10-16 | 2015-04-29 | 中国科学院物理研究所 | Lithium molybdate serving as secondary battery electrode material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241642A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Lithium molybdate cathode material for lithium ion battery and preparation method thereof |
| CN104229894A (en) * | 2013-06-17 | 2014-12-24 | 华南理工大学 | Sol-gel method for preparation of lithium ion battery lithium molybdate cathode material |
| CN104577088A (en) * | 2013-10-16 | 2015-04-29 | 中国科学院物理研究所 | Lithium molybdate serving as secondary battery electrode material |
Non-Patent Citations (2)
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| Poly(Ethylene Glycol)(PEG)-assisted shape-controlled synthesis;Mohammad Ramzan Parra等;《Optik》;20151231;第126卷(第18期);第1562-1566页 * |
| Synthesis of One Dimensional Li2MoO4 Nanostructures and Their Electrochemical Performance as Anode Materials for Lithium-ion Batteries;Xudong Liu等;《Electrochimica Acta》;20150601;第174卷;第315-326页 * |
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