CN111333041B - Framework-supported aluminum nitride non-crystallized modified lithium negative electrode material and preparation method and application thereof - Google Patents
Framework-supported aluminum nitride non-crystallized modified lithium negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery metal lithium cathode materials, and particularly relates to a framework-supported aluminum nitride non-crystallization modified lithium cathode material and a preparation method and application thereof. The preparation method takes oxygen-containing ferric salt, polyvinylpyrrolidone and carbonized melamine sponge as raw materials, and prepares the Fe-sponge base by low-temperature hydrothermal reaction and high-temperature carbonization reaction3C‑Fe3The P framework is prepared by taking oxygen acid aluminum salt as an aluminum source and carrying out high-temperature carbon thermal reaction with a carbon source to obtain AlN ultrafine particles; finally using carbon sponge base Fe3C‑Fe3And carrying out non-crystallization modification on the metal lithium by the P framework and the AlN ultrafine particles to obtain the product. The method increases the internal defects of the lithium metal negative electrode and greatly inhibits the generation of lithium metal dendrites. The noncrystallized modified metal lithium is used as the negative electrode of the lithium ion battery, so that the cycle stability of the lithium ion battery can be obviously enhanced.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a framework-supported aluminum nitride non-crystallization modified lithium negative electrode material, and a preparation method and application thereof.
Background
Electrochemical secondary batteries are one way of storing energy in the power grid. Among many electrochemical energy storage technologies, lithium ion batteries are favored for their advantages of high energy density, ultra-long cycle life, and the like. However, with the use of lithium ion batteries in large numbers in power vehicles, the cost of lithium carbonate and transition metals such as nickel and cobalt inevitably increases, and thus metal lithium with higher capacity and lower cost becomes a better choice for lithium battery materials. At present, most lithium batteries produced commercially by using metal lithium adopt organic liquid electrolytes, and the electrolytes and electrode materials are easy to generate side reactions in the charging and discharging processes, so that the battery capacity is irreversibly attenuated; meanwhile, in the long-term service process of the battery, the organic liquid electrolyte can volatilize, dry, leak and the like, and the service life of the battery is seriously influenced. On the other hand, the conventional lithium battery cannot use the metallic lithium with high energy density as a negative electrode material, and during the battery cycle, due to factors such as the surface current density of the metallic lithium and the uneven distribution of lithium ions, the metallic lithium electrode is repeatedly dissolved and deposited to form uneven holes and dendrites. The dendrite can pierce through the diaphragm to contact the positive electrode, and a series of potential safety hazards such as battery short circuit, thermal runaway, ignition and explosion are caused. Compared with the traditional lithium battery, the solid-state lithium battery has the difference that the electrolyte is solid-stated, and comprises all the units (the positive electrode, the negative electrode and the electrolyte) of the battery, the working principle of the solid-state lithium battery is the same as that of the traditional lithium battery, and the phenomena of volatilization, drying, leakage and the like of the liquid electrolyte can be avoided, but dendritic crystals can still be generated to pierce the diaphragm, so that the cycle stability of the battery is reduced.
Disclosure of Invention
The invention provides a preparation method of a framework-supported aluminum nitride amorphous modified lithium negative electrode material, aiming at the problems that a metal lithium electrode can generate dendritic crystals and the cycling stability of a lithium ion battery is poor.
The invention also provides a framework support aluminum nitride non-crystallization modified lithium negative electrode material.
The invention also provides application of the framework-supported aluminum nitride non-crystallization modified lithium negative electrode material in preparation of a lithium ion battery.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a preparation method of a framework-supported aluminum nitride non-crystallization modified lithium negative electrode material specifically comprises the following steps:
s1, carrying out hydrothermal reaction on oxygen-containing ferric salt and polyvinylpyrrolidone (PVP) at the temperature of 60-160 ℃, reacting the obtained reaction product with carbonized melamine sponge at the temperature of 100-150 ℃ to prepare a precursor, and then carrying out carbonization reaction on the precursor at the temperature of 600-900 ℃;
s2, taking an oxygen-containing acid aluminum salt as an aluminum source, uniformly mixing the aluminum source and a carbon source, and carrying out a carbothermic reaction at 1350-1650 ℃;
s3, melting the lithium metal, mixing the molten lithium metal with the product obtained in the S2 to form mixed molten metal, and pouring the mixed molten metal into a mold containing the product obtained in the S1 to obtain the lithium ion battery.
The preparation method of the invention firstly uses oxygen-containing ferric salt, polyvinylpyrrolidone and carbonized melamine sponge as raw materials, prepares an iron nitrogen phosphide precursor through low-temperature hydrothermal reaction, and then prepares carbon sponge-based iron carbide (Fe) through high-temperature carbonization reaction3C) Iron (Fe) phosphide3P) skeleton (the microstructure is shown in figure 1); then, taking oxygen acid aluminum salt as an aluminum source, and carrying out high-temperature carbon thermal reaction on the aluminum salt and a carbon source to prepare aluminum nitride (AlN) ultrafine particles (the microstructure of which is shown in figure 2); finally using carbon sponge base Fe3C-Fe3And the P framework is used as a support, and AlN ultrafine particles are used for carrying out non-crystallization modification on the metal lithium to obtain the framework-supported aluminum nitride non-crystallization modified lithium cathode material. The process flow diagram of the preparation method is shown in figure 3.
Because AlN ultrafine particles are added in the obtained material, internal defects are increased, so that metal lithium dendrites grow in the lithium negative electrode material, the generation of the metal lithium dendrites outside the metal lithium dendrites is greatly inhibited, the influence on a diaphragm is reduced, and the cycle stability of the lithium ion battery is obviously enhanced.
Preferably, the iron salt of an oxoacid is iron nitrate. The ferric nitrate may generate gas during heating, thereby enabling the formation of channels in the product.
Preferably, the mass of the polyvinylpyrrolidone is 1-9 times of that of the ferric nitrate.
Preferably, the hydrothermal reaction time in S1 is 6-36 h.
Preferably, the carbonization reaction time in S1 is 2-12 h.
Preferably, the carbonization method of the melamine sponge comprises the following steps: and (3) placing the melamine sponge in an inert atmosphere, and treating for 2-12 h at 600-900 ℃. The inert atmosphere is preferably a hydrogen-argon mixed atmosphere.
Preferably, the mass ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 1.0-1.4.
Preferably, the aluminum salt of oxyacid is a mixture of aluminum hydroxide and aluminum nitrate in a mass ratio of 2.5-3.5: 1.
Preferably, the carbon source is a mixture of sucrose and a nitrogen-containing carbon source in a mass ratio of 1.8-2.2: 1.
Preferably, the nitrogen-containing carbon source is at least one of urea or melamine.
Preferably, the carbothermal reaction is carried out in an inert atmosphere. Preferably, a nitrogen atmosphere is used.
Preferably, the carbothermic reaction time is 6-18 h.
Preferably, the step of uniformly mixing in the step S2 is to perform high-energy ball milling at 400-600 rpm for at least 24 hours.
Preferably, in S3, the mass of the product obtained in S2 is 4-6% of the mass of the lithium metal.
The embodiment of the invention also provides a framework-supported aluminum nitride non-crystallization modified lithium negative electrode material, which is prepared by the preparation method of the framework-supported aluminum nitride non-crystallization modified lithium negative electrode material.
The embodiment of the invention also provides application of the framework-supported aluminum nitride amorphization modified lithium negative electrode material in preparation of a lithium ion battery. The preparation method of the invention carries out non-crystallization modification on the metallic lithium cathode material to improve the cycle stability of the metallic lithium cathode material, and inhibits the growth of lithium dendrite, thereby having higher practical value for improving the energy density and the cycle stability of the lithium ion battery.
Drawings
FIG. 1 shows the carbon sponge base Fe obtained in the present invention S13C-Fe3The microstructure of the P framework;
FIG. 2 shows the micro-morphology of AlN ultrafine particles obtained by the S2 of the present invention;
FIG. 3 is a schematic process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a framework support AlN non-crystallization modified lithium anode material, and the preparation method comprises the following steps:
s1, mixing ferric nitrate and polyvinylpyrrolidone serving as raw materials according to a mass ratio of 1:2.0, dissolving in deionized water, and reacting for 6 hours at 55 ℃ under the condition of magnetic stirring; then transferring the uniformly dispersed solution into a hydrothermal reaction kettle, and putting carbonized melamine sponge (the treatment conditions of the melamine sponge are argon-hydrogen mixed atmosphere, the carbonization temperature is 750 ℃ and the carbonization time is 12 hours) into the reaction kettle in advance; then placing the reaction kettle in a drying oven, and reacting for 24 hours at 120 ℃ to obtain a carbon-phosphorus-iron compound precursor; finally, the prepared carbon-phosphorus-iron compound precursor is subjected to carbonization reaction in a tubular sintering furnace in nitrogen atmosphere at the carbonization temperature of 800 ℃ for 10h to finally prepare the carbon sponge base Fe3C-Fe3And (3) a P framework.
S2, mixing aluminum hydroxide and aluminum nitrate serving as aluminum sources, sucrose and urea serving as carbon sources according to the mass ratio of Al to C of 1:1.2 (wherein the mass ratio of the aluminum hydroxide to the aluminum nitrate is 3:1, and the mass ratio of the sucrose to the urea is 2:1), and placing the mixture in a high-energy ball mill with 500rpm for processing for 24 hours; and then placing the material in a sintering furnace in a circulating nitrogen atmosphere for carbothermic reaction at 1500 ℃ for 12 hours to finally prepare the AlN ultrafine particles with uniform particle size.
S3, completely melting lithium metal under the protection of nitrogen atmosphere at 150 ℃, adding the prepared AlN ultrafine particles (accounting for 5 percent of the mass of the lithium metal), and mechanically stirring to prepare uniformMolten metal, and finally pouring the molten metal into the iron core with the carbon sponge base Fe placed in advance3C-Fe3Forming the P framework in a die to prepare the carbon sponge base Fe3C-Fe3And P supports the AlN non-crystallization modified lithium cathode material.
Example 2
The embodiment provides a framework support AlN non-crystallization modified lithium anode material, and the preparation method comprises the following steps:
s1, mixing ferric nitrate and polyvinylpyrrolidone serving as raw materials according to a mass ratio of 1:1, dissolving in deionized water, and reacting for 12 hours at 85 ℃ under the condition of magnetic stirring; then transferring the uniformly dispersed solution into a hydrothermal reaction kettle, and putting carbonized melamine sponge (the treatment conditions of the melamine sponge are argon-hydrogen mixed atmosphere, the carbonization temperature is 600 ℃ and the carbonization time is 12 hours) into the reaction kettle in advance; then placing the reaction kettle in a drying oven, and reacting for 24 hours at 120 ℃ to obtain a carbon-phosphorus-iron compound precursor; finally, the prepared carbon-phosphorus-iron compound precursor is subjected to carbonization reaction in a tubular sintering furnace in nitrogen atmosphere at the carbonization temperature of 600 ℃ for 12h to finally prepare the carbon sponge base Fe3C-Fe3And (3) a P framework.
S2, mixing aluminum hydroxide and aluminum nitrate serving as aluminum sources, sucrose and urea serving as carbon sources according to the mass ratio of Al to C of 1:1.3 (wherein the mass ratio of the aluminum hydroxide to the aluminum nitrate is 2.5:1, and the mass ratio of the sucrose to the urea is 1.9:1), and placing the mixture in a high-energy ball mill at 500rpm for processing for 24 hours; and then placing the material in a sintering furnace in a flowing nitrogen atmosphere for carbothermic reaction at 1400 ℃ for 12 hours to finally prepare the AlN ultrafine particles with uniform particle size.
S3, completely melting lithium metal at 150 ℃ under the protection of nitrogen atmosphere, adding pre-prepared AlN ultrafine particles (accounting for 6 percent of the mass of the lithium metal), mechanically stirring to prepare uniform metal liquid, and finally pouring the metal liquid into a pre-placed carbon sponge base Fe3C-Fe3Forming the P framework in a die to prepare the carbon sponge base Fe3C-Fe3And P supports the AlN non-crystallization modified lithium cathode material.
Example 3
The embodiment provides a framework support AlN non-crystallization modified lithium anode material, and the preparation method comprises the following steps:
s1, mixing ferric nitrate and polyvinylpyrrolidone serving as raw materials according to a mass ratio of 1:4, dissolving in deionized water, and reacting for 24 hours under the condition of magnetic stirring at 100 ℃; then transferring the uniformly dispersed solution into a hydrothermal reaction kettle, and putting carbonized melamine sponge (the treatment conditions of the melamine sponge are argon-hydrogen mixed atmosphere, the carbonization temperature is 900 ℃ and the carbonization time is 2 hours) into the reaction kettle in advance; then placing the reaction kettle in a drying oven, and reacting for 24 hours at 120 ℃ to obtain a carbon-phosphorus-iron compound precursor; finally, the prepared carbon-phosphorus-iron compound precursor is subjected to carbonization reaction in a tubular sintering furnace in nitrogen atmosphere at the carbonization temperature of 900 ℃ for 2 hours to finally prepare the carbon sponge base Fe3C-Fe3And (3) a P framework.
S2, mixing aluminum hydroxide and aluminum nitrate serving as aluminum sources, sucrose and urea serving as carbon sources according to the mass ratio of Al to C of 1:1.0 (wherein the mass ratio of the aluminum hydroxide to the aluminum nitrate is 3.5:1, and the mass ratio of the sucrose to the urea is 1.8:1), and placing the mixture in a high-energy ball mill at 500rpm for processing for 24 hours; and then placing the material in a sintering furnace in a circulating nitrogen atmosphere for carbothermal reaction at 1350 ℃ for 12 hours to finally prepare the AlN ultrafine particles with uniform particle size.
S3, completely melting lithium metal at 150 ℃ under the protection of nitrogen atmosphere, adding pre-prepared AlN ultrafine particles (accounting for 4% of the mass of the lithium metal), mechanically stirring to prepare uniform metal liquid, and finally pouring the metal liquid into a pre-placed carbon sponge base Fe3C-Fe3Forming the P framework in a die to prepare the carbon sponge base Fe3C-Fe3And P supports the AlN non-crystallization modified lithium cathode material.
Example 4
The embodiment provides a framework support AlN non-crystallization modified lithium anode material, and the preparation method comprises the following steps:
s1, taking ferric nitrate and polyvinylpyrrolidone as raw materials according to the qualityProportioning materials according to the weight ratio of 1:7, dissolving in deionized water, and reacting for 6 hours at 160 ℃ under the condition of magnetic stirring; then transferring the uniformly dispersed solution into a hydrothermal reaction kettle, and putting carbonized melamine sponge (the treatment conditions of the melamine sponge are argon-hydrogen mixed atmosphere, the carbonization temperature is 800 ℃ and the carbonization time is 10 hours) into the reaction kettle in advance; then placing the reaction kettle in a drying oven, and reacting for 24 hours at 120 ℃ to obtain a carbon-phosphorus-iron compound precursor; finally, the prepared carbon-phosphorus-iron compound precursor is subjected to carbonization reaction in a tubular sintering furnace in nitrogen atmosphere at the carbonization temperature of 700 ℃ for 4h to finally prepare the carbon sponge base Fe3C-Fe3And (3) a P framework.
S2, mixing aluminum hydroxide and aluminum nitrate serving as aluminum sources, sucrose and urea serving as carbon sources according to the mass ratio of Al to C of 1:1.1 (wherein the mass ratio of the aluminum hydroxide to the aluminum nitrate is 2.7:1, and the mass ratio of the sucrose to the urea is 2.1:1), and placing the mixture in a high-energy ball mill at 500rpm for processing for 24 hours; and then placing the material in a sintering furnace in a circulating nitrogen atmosphere for carbothermic reaction at 1550 ℃ for 12 hours to finally prepare the AlN ultrafine particles with uniform particle size.
S3, completely melting lithium metal at 150 ℃ under the protection of nitrogen atmosphere, adding pre-prepared AlN ultrafine particles (accounting for 4.5 percent of the mass of the lithium metal), mechanically stirring to prepare uniform metal liquid, and finally pouring the metal liquid into a pre-placed carbon sponge base Fe3C-Fe3Forming the P framework in a die to prepare the carbon sponge base Fe3C-Fe3And P supports the AlN non-crystallization modified lithium cathode material.
Example 5
The embodiment provides a framework support AlN non-crystallization modified lithium anode material, and the preparation method comprises the following steps:
s1, mixing ferric nitrate and polyvinylpyrrolidone serving as raw materials according to a mass ratio of 1:9, dissolving in deionized water, and reacting for 36 hours at 60 ℃ under the condition of magnetic stirring; then transferring the uniformly dispersed solution into a hydrothermal reaction kettle, and putting carbonized melamine sponge (melamine sponge treatment conditions) into the reaction kettle in advanceComprises the following steps: argon-hydrogen mixed atmosphere, carbonization temperature of 750 ℃ and carbonization time of 4 h); then placing the reaction kettle in a drying oven, and reacting for 24 hours at 120 ℃ to obtain a carbon-phosphorus-iron compound precursor; finally, the prepared carbon-phosphorus-iron compound precursor is subjected to carbonization reaction in a tubular sintering furnace in nitrogen atmosphere at the carbonization temperature of 800 ℃ for 6 hours to finally prepare the carbon sponge base Fe3C-Fe3And (3) a P framework.
S2, mixing aluminum hydroxide and aluminum nitrate serving as aluminum sources, sucrose and urea serving as carbon sources according to the mass ratio of Al to C of 1:1.4 (wherein the mass ratio of the aluminum hydroxide to the aluminum nitrate is 3.3:1, and the mass ratio of the sucrose to the urea is 2.2:1), and placing the mixture in a high-energy ball mill at 500rpm for processing for 24 hours; and then placing the material in a sintering furnace in a flowing nitrogen atmosphere for carbothermic reaction at 1650 ℃ for 12 hours to finally prepare the AlN ultrafine particles with uniform particle size.
S3, completely melting lithium metal at 150 ℃ under the protection of nitrogen atmosphere, adding pre-prepared AlN ultrafine particles (accounting for 5.5 percent of the mass of the lithium metal), mechanically stirring to prepare uniform metal liquid, and finally pouring the metal liquid into a pre-placed carbon sponge base Fe3C-Fe3Forming the P framework in a die to prepare the carbon sponge base Fe3C-Fe3And P supports the AlN non-crystallization modified lithium cathode material.
Example 6
The embodiment provides application of a framework-supported AlN non-crystallization modified lithium negative electrode material in preparation of a lithium ion battery.
The framework-supported AlN non-crystallized modified lithium negative electrode material prepared in example 1 was assembled into a battery at 1.5mAcm-2The polarization voltage is lower than 30mV after the current density is cycled for 800h, and good cycle stability is shown.
The framework-supported AlN non-crystallized modified lithium negative electrode material prepared in example 1 was assembled into a battery at 1mAcm-2The polarization voltage is lower than 28mV after the current density is cycled for 1000 hours, and the good cycle stability is also shown.
With LiNi0.6Co0.2Mn0.2O2Is a positive electrodeA C2032 coin cell is assembled by using the framework-supported AlN amorphous modified lithium cathode material prepared in the example 1 as a cathode, wherein the charging and discharging voltage platform is 2.8-4.3V, and the current density is 200 mA.g-1The first discharge capacity is 178.6mAh g-1The specific charge-discharge capacity of the previous 10 cycles is 165.8mAh g-1And the capacity retention rate after 500 cycles is 94.7%.
With LiNi0.8Co0.1Mn0.1O2The framework-supported AlN non-crystallized modified lithium negative electrode material prepared in example 1 is used as a negative electrode, a C2032 button cell is assembled, the charge-discharge voltage platform is 2.8-4.3V, and the first discharge capacity is 210.5mAh g-1And the capacity retention rate after 500 cycles is 90.5%.
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 or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a framework-supported aluminum nitride non-crystallization modified lithium negative electrode material is characterized by comprising the following steps:
s1, carrying out hydrothermal reaction on oxygen-containing ferric salt and polyvinylpyrrolidone at the temperature of 60-160 ℃, reacting the obtained reaction product with carbonized melamine sponge at the temperature of 100-150 ℃ to prepare a precursor, and then carrying out carbonization reaction on the precursor at the temperature of 600-900 ℃;
s2, taking an oxygen-containing acid aluminum salt as an aluminum source, uniformly mixing the aluminum source and a carbon source, and carrying out a carbothermic reaction at 1350-1650 ℃;
s3, melting the lithium metal, mixing the molten lithium metal with the product obtained in the S2 to form mixed molten metal, and pouring the mixed molten metal into a mold containing the product obtained in the S1 to obtain the lithium ion battery.
2. The method for preparing the amorphous modified lithium cathode material of framework-supported aluminum nitride according to claim 1, wherein the iron salt containing oxygen acid is ferric nitrate.
3. The preparation method of the framework-supported aluminum nitride amorphized modified lithium anode material as claimed in claim 2, wherein the mass of the polyvinylpyrrolidone is 1-9 times that of the iron nitrate.
4. The preparation method of the framework-supported aluminum nitride amorphous modified lithium anode material as claimed in claim 1, wherein the hydrothermal reaction time in S1 is 6-36 h; and/or
The carbonization reaction time in S1 is 2-12 h; and/or
The carbonization method of the melamine sponge comprises the following steps: and (3) placing the melamine sponge in an inert atmosphere, and treating for 2-12 h at 600-900 ℃.
5. The method for preparing the framework-supported aluminum nitride amorphization-modified lithium anode material as claimed in claim 1, wherein the mass ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 1.0-1.4; and/or
The oxygen acid aluminum salt is a mixture of aluminum hydroxide and aluminum nitrate in a mass ratio of 2.5-3.5: 1; and/or
The carbon source is a mixture of sucrose and a nitrogen-containing carbon source in a mass ratio of 1.8-2.2: 1.
6. The preparation method of the framework-supported aluminum nitride amorphization-modified lithium anode material as claimed in claim 5, wherein the nitrogen-containing carbon source is at least one of urea or melamine.
7. The preparation method of the framework-supported aluminum nitride amorphized modified lithium anode material as claimed in claim 1, wherein the carbothermic reaction is carried out in an inert atmosphere; and/or
The carbothermic reaction time is 6-18 h; and/or
And in the step S2, the uniform mixing is carried out by high-energy ball milling at 400-600 rpm for at least 24 h.
8. The preparation method of the framework-supported aluminum nitride amorphized modified lithium anode material as claimed in claim 1, wherein in S3, the mass of the product obtained in S2 is 4-6% of the mass of the metal lithium.
9. The framework-supported aluminum nitride non-crystallization modified lithium negative electrode material is characterized by being prepared by the preparation method of the framework-supported aluminum nitride non-crystallization modified lithium negative electrode material according to any one of claims 1 to 8.
10. The use of the framework-supported aluminum nitride amorphized modified lithium anode material of claim 9 in the preparation of a lithium ion battery.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435371A (en) * | 2003-03-12 | 2003-08-13 | 北京科技大学 | Method for preparing aluminium nitride powder |
| CN107799736A (en) * | 2017-09-22 | 2018-03-13 | 山东大学 | A kind of lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation and preparation method thereof |
| CN108461724A (en) * | 2018-03-05 | 2018-08-28 | 苏州大学 | A kind of preparation method of high security metal composite negative pole |
| CN109559898A (en) * | 2018-11-09 | 2019-04-02 | 江苏大学 | A kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100624950B1 (en) * | 2004-10-18 | 2006-09-15 | 삼성에스디아이 주식회사 | Battery outer case having heat spreading layer and lithium polymer battery using it |
-
2020
- 2020-02-24 CN CN202010112674.6A patent/CN111333041B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435371A (en) * | 2003-03-12 | 2003-08-13 | 北京科技大学 | Method for preparing aluminium nitride powder |
| CN107799736A (en) * | 2017-09-22 | 2018-03-13 | 山东大学 | A kind of lithium metal composite negative pole of three-dimensional self-supporting parent lithium carrier encapsulation and preparation method thereof |
| CN108461724A (en) * | 2018-03-05 | 2018-08-28 | 苏州大学 | A kind of preparation method of high security metal composite negative pole |
| CN109559898A (en) * | 2018-11-09 | 2019-04-02 | 江苏大学 | A kind of preparation method of the carbon sponge flexible composite of cobalt sulfide iron nanotube load |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| Porous Carbon Spheres Doped with Fe3C as an Anode for High-Rate Lithium-ion Batteries;Shouhui Chen et al.;《Electrochimica Acta》;20150822;第180卷;说明书第2页第14行至第23行 * |
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| CN111333041A (en) | 2020-06-26 |
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