CN111864203A - High-capacitance lithium-carbon negative electrode material and preparation method and application thereof - Google Patents
High-capacitance lithium-carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a high-capacitance lithium electrical carbon negative electrode material, a preparation method and application thereof, wherein the lithium electrical carbon negative electrode material is a conductive fiber carbon material, and the preparation method comprises the following steps: placing organic fibers in a protective atmosphere, pre-sintering at 300-800 ℃, carbonizing at 500-1200 ℃, and cooling to room temperature to obtain the conductive fiber carbon material; the temperature of the carbonization treatment is higher than the temperature of pre-sintering; the organic fiber is at least one of polyacrylonitrile fiber, viscose fiber and asphalt fiber, preferably at least one of spandex, terylene, vinylon, aramid fiber, polybenzimidazole PBI fiber and polyimide PI fiber.
Description
Technical Field
The invention relates to a lithium battery negative electrode material and a preparation method and application thereof, in particular to a lithium battery carbon negative electrode material and a preparation method and application thereof, and belongs to the technical field of lithium battery electrode materials.
Background
In the early 90 s of the 20 th century, Sony corporation introduced the first commercial lithium ion battery (C/LiCoO)2) The capacity of 18650 type lithium ion batteries is increased from 1200 to 2200-2600 mAh, the composition and the capacity of a positive electrode material are not changed too much, and the increase of the battery capacity mainly comes from the contribution of a negative electrode material.
At present, the cathode material of commercial lithium ion batteries is mainly made of carbon materials, and has high specific capacity (200-400 mAh.g)-1) Low electrode potential (< 1.0V vs Li)+Li), good cycle performance (over 1000 weeks), stable cycle performance. Carbon materials can be classified into two major types, graphite materials and amorphous carbon materials, according to the degree of crystallization. The graphite material has the characteristics of good conductivity, high crystallinity, stable layered structure, suitability for lithium intercalation-deintercalation and the like, and becomes an ideal lithium battery negative electrode material, and artificial graphite and natural graphite are two main graphite materials. While amorphous carbon materials, i.e., carbon materials without fixed crystalline shapes, mainly include soft carbon and hard carbon. Silicon-based materials, transition metal oxides and sulfides, and some alloy materials, which are not carbon-based negative electrode materials, have a high theoretical capacity, and thus have received attention from many researchers. However, two problems are generally existed in the practical application of the non-carbon materials: firstly, poor cycle stability: when lithium ions are inserted into the material, huge volume expansion (400%) can be generated in the alloying process, and the repeated insertion/extraction of the lithium ions can easily lead the crystal structure of the material to be pulverized and agglomerated, and finally the attenuation of the electrochemical performance is initiated; secondly, deviation of high-rate performance of the battery: generally, the metal oxide is a poor electric conductor, a large amount of conductive agent needs to be added in the process of preparing the electrode, when the charge-discharge current density is increased, a rapid transmission channel of ions and electrons cannot be formed, and the electrochemical performance can be rapidly improved And (4) attenuation. Therefore, research and development on non-carbon negative electrode materials are mainly focused on how to improve the conductivity of the non-carbon negative electrode materials, inhibit volume change generated in the lithium ion alloying process, prevent pulverization, collapse and agglomeration of the material structure, and the like.
The commercial development research on the lithium ion battery negative electrode material focuses on the aspects of improving the first charge-discharge coulombic efficiency, increasing the mass and volume specific capacity, prolonging the cycle life, reducing the cost and the like. At present, most of the negative electrode materials used in commercial lithium ion batteries are carbon materials, including artificial/natural graphite, petroleum coke, mesocarbon microbeads (MCMB), and the like. The carbon material as the cathode material has the advantages of lower electrode potential, good lithium intercalation/deintercalation capability, good cycle stability and the like. However, the biggest defect of the lithium ion battery is that the capacity is low, the theoretical specific capacity is only 372m Ah g-1, the capacity is only about 200mAh g-1 in actual use, and obviously, the high-capacity high-rate performance requirement of the modern lithium ion battery cannot be met.
Thus, prior art research into carbon-based materials has focused primarily on improving its lithium storage capacity and high rate performance. In addition, among many special morphologies, the fibrous carbon structure can effectively increase the specific surface area of the material to fully utilize the active material, and can shorten the migration path of lithium ions in the material to improve the rate capability of the material, so that the fibrous carbon structure is a great research hotspot in the field of materials in recent years. However, the carbon material obtained by sintering the existing organic fiber has the problems of low first effect, poor stability and the like, and the specific capacity of the carbon material is lower than the theoretical value.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a high-capacity lithium battery carbon negative electrode material, and a preparation method and an application thereof, so as to improve electrochemical properties of a lithium battery, such as specific capacity, cycling stability, and the like.
In one aspect, the invention provides a preparation method of a lithium battery carbon negative electrode material, wherein the lithium battery carbon negative electrode material is a conductive fiber carbon material, and the preparation method comprises the following steps: placing organic fibers in a protective atmosphere, pre-sintering at 300-600 ℃, carbonizing at 500-1200 ℃, and cooling to room temperature to obtain the conductive fiber carbon material; the temperature of the carbonization treatment is higher than the temperature of pre-sintering; the organic fiber is at least one of polyacrylonitrile fiber, viscose fiber and asphalt fiber, preferably at least one of spandex, terylene, vinylon, aramid fiber, polybenzimidazole PBI fiber and polyimide PI fiber.
In the disclosure, polyacrylonitrile-based fibers, viscose fibers, pitch fibers and the like (for example, spandex, terylene, vinylon, aramid fibers, polybenzimidazole PBI fibers, polyimide PI fibers and the like) are used as raw materials of conductive fiber carbon materials, the raw materials are placed in a protective atmosphere, the raw materials are pre-sintered at 300-600 ℃, and unstable hydroxyl, aldehyde group, amino group and the like on the surface of the fibers are removed in the process to form a stable fiber framework structure. And then carbonizing at 500-1200 ℃, forming a stable graphite microcrystal structure in the process, removing unstable carbon-oxygen functional groups, forming a stable high-conductivity fiber carbon material, and finally cooling to room temperature to obtain the conductive fiber carbon material with the structure, the appearance, the property, the lithium electric capacity and the like completely different from those of the existing material.
Preferably, the diameter of the organic fiber is 30 to 80 μm, and the length is 200 to 20000 μm.
Preferably, the protective atmosphere is an inert atmosphere, and the inert atmosphere is an argon atmosphere.
Preferably, the pre-sintering temperature is more than 400 ℃ and less than or equal to 600 ℃, and the raw material can remove unstable groups such as hydroxyl, amino and the like adsorbed on the surface of the fiber at this stage, so that the structure is more stable.
Preferably, the pre-sintering time is 2-5 hours.
Preferably, the temperature rise rate of the pre-sintering is 5-10 ℃/min.
Preferably, the temperature of the carbonization treatment is 500-1200 ℃.
Preferably, the carbonization time is 2 to 10 hours.
Preferably, the temperature rise rate of the carbonization treatment is 5 to 10 ℃/min.
Preferably, the temperature is reduced to room temperature after 2-10 hours after the carbonization treatment, so as to prevent fiber breakage and surface cracks caused by too fast temperature reduction.
In another aspect, the invention provides a lithium battery carbon negative electrode material prepared according to the preparation method.
In still another aspect, the present invention provides a carbon fiber lithium battery comprising the above-described lithium electrical carbon negative electrode material.
The invention has the advantages that:
The carbon material with high capacity is synthesized by adopting simple and direct one-step carbonization, taking the carbon fiber as a carbon source and performing one-step carbonization, and the carbon material serving as the negative electrode material of the lithium ion battery has high specific capacity, good rate capability and cycling stability, cheap and easily available raw materials, simple preparation process and hopeful realization of large-scale production. The prepared lithium battery negative electrode material has higher capacity (350 mAh/g). The carbon fiber material has the advantages of high conductivity, improved specific capacity, low impedance, and improved stability.
Drawings
Fig. 1 is an SEM image of the lithium battery carbon negative electrode material synthesized in example 1;
fig. 2 is a plot of cyclic voltammetry curves for experimental button lithium batteries prepared in example 1;
fig. 3 is a graph of charge and discharge performance at constant current density for an experimental button lithium battery prepared in example 1;
fig. 4 is a graph of the cycle life curve of the experimental lithium button cell prepared in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, a lithium battery negative electrode material (lithium battery carbon negative electrode material) is provided that is a conductive fibrous carbon material (i.e., carbon fiber). The carbon fiber is prepared by pre-oxidizing, carbonizing and other high temperature solid phase reaction process of nitrile fiber, viscose fiber, asphalt fiber and other precursor fiber with high carbon content (more than 90%). The obtained carbon material is composed of graphite microcrystals with preferred orientation, so that the carbon material has good conductivity and lithium electric capacity.
According to the invention, organic fibers are used as raw materials, and the processes of temperature rise, constant temperature and temperature reduction are carried out according to the set curve, so that the high-capacity conductive fibrous carbon material is prepared. The following exemplarily illustrates a method for preparing a negative electrode material for a lithium battery.
Weighing the organic fibers, and putting the organic fibers into a tubular furnace containing protective atmosphere for presintering. Wherein the protective atmosphere may be argon. The pre-sintering temperature can be 300-600 ℃, and the time can be 2-5 hours. As a detailed example, the pre-sintering temperature curve in an argon-protected furnace is set to be heated to 300-500 ℃ from room temperature at the speed of 5-10 ℃/min, and the temperature is kept for 2-5 hours.
And further carbonizing the organic fiber after the pre-sintering. The carbonization treatment is also carried out in a protective atmosphere. Wherein the protective atmosphere may be argon. For example, the temperature of the carbonization treatment is controlled to 500-1200 ℃ in an argon protection furnace and is kept for 2-10 hours. The temperature rise rate of the carbonization treatment can be 5-10 ℃/min.
And cooling to room temperature after carbonization treatment. For example, the temperature is reduced from the carbonization temperature (500-1200 ℃) to room temperature within 5-10 hours in an argon atmosphere.
The carbon fiber material prepared by pre-oxidizing and carbonizing organic fibers (spandex, terylene, vinylon, aramid fiber, PBI (polybenzimidazole), PI (polyimide) and the like) is applied to the preparation of the lithium battery. The obtained carbon fiber material has good stability and higher conductivity within a proper voltage range (0-1.0V). And after the lithium battery prepared from the carbon fiber material is cycled for 100 times, the capacity retention rate of the lithium battery is still over 93%.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
High capacity conductive fibrous carbon material, sample synthesis:
weighing aramid fiber 1414 well; loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: raising the temperature from room temperature to 500 ℃ at a speed of 5 ℃/min and keeping the temperature for 2 hours, then raising the temperature to 900 ℃ at a speed of 5 ℃/min in an argon protection furnace and keeping the temperature for 10 hours, and reducing the temperature from 900 ℃ to room temperature in an argon atmosphere for 5 hours. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material.
And (3) testing electrical properties:
the prepared lithium battery electrode is measured for capacitance value, specific capacitance, energy density and power density by using cyclic voltammetry and constant current step method on Shanghai Hua CHI660D electrochemical workstation. The sweep rate of cyclic voltammetry is 0.002V/s, the voltage test range is 0V to 1.0V, and the current of the constant current step method is 3 mA.
Preparation of lithium battery (carbon fiber lithium battery): dissolving 10% of polyvinylidene fluoride (PVDF) in mass percent in N-2 methyl pyrrolidone (NMP), stirring until the polyvinylidene fluoride is completely dissolved, then pouring 80% of conductive carbon fibers and 10% of conductive acetylene black in mass percent into the slurry, stirring at a high speed for 12 hours until the active material is completely dissolved, enabling the slurry to be in a black colloid shape, uniformly coating 20 mu L of the slurry on a current collector, flatly placing the coated electrode plate in a drying box, baking for 5min at 120 ℃ to completely volatilize the N-2 methyl pyrrolidone, and coating the slurry on the current collector by using conductive adhesive (PVDF: NMP: acetylene black is 5 mg: 1 ml: 50 mg). And placing the isolating membrane between the pole piece and the lithium piece, stacking the pole piece and the lithium piece in order, contacting one surface of the pole piece coated with the active material with the diaphragm, sealing the isolating membrane and the electrode piece by adopting a packaging shell, and filling the prepared electrolyte to obtain the experimental button lithium battery containing the carbon electrode.
And assembling the obtained product serving as an electrode material into an experimental button lithium battery in a glove box filled with argon. Then, the carbon fiber is subjected to charge-discharge circulation at the multiplying power of 1C between 0 and 1.0V, and the first discharge capacity of the carbon fiber is 350mAh g-1(as shown in FIG. 2), the reversible capacity of 1C rate charge and discharge after 100 weeks of cycle still reaches 346mAh g-1Experimental button lithium cells made of carbon fiber material showed excellent cycle life performance (as shown in fig. 4).
FIG. 1 is a SEM image of the surface morphology and chemical composition of the conductive fibrous carbon material prepared in example 1, wherein the SEM image shows the fibrous morphology of the carbon fiber, the diameter of the carbon fiber is 30-80 μm, the length of the carbon fiber is 200-20000 μm, and the morphology of the carbon fiber is kept smooth and intact and is not damaged. The performance of the electrode lithium battery is researched by adopting a cyclic voltammetry method and a constant-current charging and discharging method. The cyclic voltammetry test results of fig. 2 show that the CV curve of the corresponding button lithium battery shows a significant redox peak, which is the mark of hard carbon. The constant current step curve (it curve) in FIG. 3 shows that the capacitance of the carbon fiber electrode prepared by the invention reaches 350mAh g-1Capacity of 320mAh g compared to commercial hard carbon (Japanese Wuyu) lithium battery-1And is also high, closer to the theoretical value. FIG. 4 is a graph comparing the cycle life curves at sweep rate of 2mV/s for 100 cycles, showing better reversibility and high capacity.
Example 2
High capacity conductive fibrous carbon material, sample synthesis:
weighing terylene; loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: heating to 600 deg.C from 10 deg.C/min at room temperature for 2 hr, heating to 800 deg.C at 5 deg.C/min in an argon-protected furnace, maintaining for 10 hr, and cooling to room temperature from 800 deg.C for 5 hr in argon atmosphere. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 3
High capacity conductive fibrous carbon material, sample synthesis:
weighing vinylon; loading into a tube furnace for presintering and carbonizing treatment. Setting the temperature curve in the sintering furnace under the protection of argon: raising the temperature from room temperature to 500 ℃ at a speed of 5 ℃/min, keeping the temperature for 1 hour, raising the temperature to 1100 ℃ at a speed of 10 ℃/min in an argon protection furnace, keeping the temperature for 5 hours, and finally cooling the temperature to room temperature from 1100 ℃ for 5 hours in an argon atmosphere. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 4
High capacity conductive fibrous carbon material, sample synthesis:
weighing aramid fibers 1313; loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: raising the temperature from 5 ℃/min to 600 ℃ at room temperature for 2 hours, raising the temperature to 900 ℃ at 10 ℃/min in an argon protection furnace, preserving the temperature for 5 hours, and reducing the temperature from 900 ℃ to room temperature in an argon atmosphere for 5 hours. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 5
High capacity conductive fibrous carbon material, sample synthesis:
PBI (polybenzimidazole) is weighed; loading into a tube furnace for presintering and carbonizing treatment. Temperature profile in an argon-protected sintering furnace: raising the temperature from room temperature to 600 ℃ at the speed of 5 ℃/min for 3 hours, raising the temperature to 900 ℃ in a furnace protected by argon at the speed of 5 ℃/min, preserving the temperature for 10 hours, and reducing the temperature from 900 ℃ to room temperature in an argon atmosphere. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 6
High capacity conductive fibrous carbon material, sample synthesis:
weighing PI (polyimide); loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: : raising the temperature from room temperature to 500 ℃ at the temperature of 5 ℃/min for 2 hours, raising the temperature to 900 ℃ in a furnace protected by argon at the temperature of 5 ℃/min, preserving the temperature for 10 hours, and reducing the temperature from 900 ℃ to room temperature in the argon atmosphere. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 7
High capacity conductive fibrous carbon material, sample synthesis:
weighing vinylon; loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: raising the temperature from 5 ℃/min to 600 ℃ at room temperature for 2 hours, then raising the temperature to 900 ℃ at 10 ℃/min in an argon protection furnace, preserving the temperature for 6 hours, and reducing the temperature to the room temperature at 900 ℃ in an argon atmosphere for 10 hours. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 8
High capacity conductive fibrous carbon material, sample synthesis:
weighing aramid fibers 1313; loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: heating from room temperature 10 deg.C/min to 500 deg.C for 1 hr, heating to 900 deg.C at 5 deg.C/min in an argon protected furnace, maintaining for 5 hr, and cooling from 900 deg.C to room temperature in argon atmosphere for 10 hr. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 9
High capacity conductive fibrous carbon material, sample synthesis:
weighing aramid fiber 1414 well; loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: raising the temperature from room temperature to 600 ℃ at the speed of 5 ℃/min for 2 hours, raising the temperature to 900 ℃ in a furnace protected by argon at the speed of 5 ℃/min, preserving the temperature for 5 hours, and reducing the temperature from 900 ℃ to room temperature in the argon atmosphere. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Example 10
High capacity conductive fibrous carbon material, sample synthesis:
PBI (polybenzimidazole) is weighed; loading into a tube furnace for presintering and carbonizing treatment. Setting the sintering temperature curve in an argon protected furnace: raising the temperature from room temperature to 500 ℃ at the temperature of 5 ℃/min for 2 hours, raising the temperature to 900 ℃ in a furnace protected by argon at the temperature of 5 ℃/min, preserving the temperature for 10 hours, and reducing the temperature from 900 ℃ to room temperature in the argon atmosphere. And (4) carrying out heating, constant temperature and cooling processes according to the set curve to obtain the high-capacity conductive fiber carbon material. Experimental button lithium batteries were prepared using the resulting conductive fibrous carbon material, the method of preparation and the method of performance testing were described in example 1, and the data of performance testing is shown in table 1.
Table 1 shows the raw materials and performance parameters of the conductive fibrous carbon materials prepared in examples 1 to 10 of the present invention:
Claims (10)
1. a preparation method of a lithium battery carbon negative electrode material is characterized in that the lithium battery carbon negative electrode material is a conductive fiber carbon material, and the preparation method comprises the following steps: placing organic fibers in a protective atmosphere, pre-sintering at 300-800 ℃, carbonizing at 500-1200 ℃, and cooling to room temperature to obtain the conductive fiber carbon material; the temperature of the carbonization treatment is higher than the temperature of pre-sintering; the organic fiber is at least one of polyacrylonitrile fiber, viscose fiber and asphalt fiber, preferably at least one of spandex, terylene, vinylon, aramid fiber, polybenzimidazole PBI fiber and polyimide PI fiber.
2. The method according to claim 1, wherein the organic fiber has a diameter of 30 to 80 μm and a length of 200 to 20000 μm.
3. The method according to claim 1 or 2, wherein the protective atmosphere is an inert atmosphere, and the inert atmosphere is an argon atmosphere.
4. The method according to any one of claims 1 to 3, wherein the temperature of the pre-sintering is > 400 ℃ and ≤ 600 ℃.
5. The production method according to any one of claims 1 to 4, wherein the temperature increase rate of the pre-sintering is 5 to 10 ℃/min.
6. The production method according to any one of claims 1 to 5, wherein the pre-sintering time is 2 to 5 hours; the carbonization treatment time is 2-10 hours.
7. The production method according to any one of claims 1 to 6, wherein the temperature increase rate of the carbonization treatment is 5 to 10 ℃/min.
8. The method according to any one of claims 1 to 7, wherein the temperature is lowered to room temperature after the carbonization treatment for 2 to 10 hours.
9. A lithium battery carbon negative electrode material prepared according to the preparation method of any one of claims 1 to 8.
10. A carbon fiber lithium battery comprising the lithium battery carbon negative electrode material of claim 9.
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| CN113346076A (en) * | 2021-05-14 | 2021-09-03 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159421A (en) * | 1995-11-24 | 1997-09-17 | 丸善石油化学株式会社 | Porous carbon material containing minute pores, and process for preparing the same |
| CN101066757A (en) * | 2007-05-11 | 2007-11-07 | 东华大学 | Process of preparing asphalt carbon foam material |
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN103311519A (en) * | 2012-03-07 | 2013-09-18 | 上海杉杉科技有限公司 | Composite hard carbon negative electrode material, and preparation method and application thereof |
| JP5456392B2 (en) * | 2009-07-09 | 2014-03-26 | 国立大学法人三重大学 | Negative electrode material for lithium ion secondary battery and lithium ion secondary battery |
| CN103806129A (en) * | 2014-02-19 | 2014-05-21 | 中国科学院化学研究所 | Nitrogen-doped porous carbon fiber material and preparation method and application thereof |
| CN103811737A (en) * | 2014-03-03 | 2014-05-21 | 杭州师范大学 | Preparation method of high-performance flexible lithium ion battery electrode material |
| CN103855361A (en) * | 2014-03-28 | 2014-06-11 | 清华大学 | Method for preparing nitrogen-doped porous carbon nanofiber cloth |
| CN105565297A (en) * | 2014-10-13 | 2016-05-11 | 徐海波 | Graphene quantum dot prepared from tip surface of carbon fiber through electrochemical oxidation and cutting, and preparation method thereof |
| CN106486673A (en) * | 2015-08-25 | 2017-03-08 | 神华集团有限责任公司 | Material with carbon element for lithium ion battery negative and preparation method thereof and lithium ion battery negative and lithium ion battery |
| CN106654190A (en) * | 2016-11-04 | 2017-05-10 | 华中科技大学 | One-dimensional In<2>O<3>/C fiber composite material, and preparation method and application thereof |
| CN106941167A (en) * | 2017-04-17 | 2017-07-11 | 中航锂电（洛阳）有限公司 | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof |
| CN108270007A (en) * | 2017-01-03 | 2018-07-10 | 神华集团有限责任公司 | Carbon raw material composition and its application and carbon material and its preparation method and application and negative electrode of lithium ion battery and lithium ion battery |
-
2019
- 2019-04-28 CN CN201910351610.9A patent/CN111864203B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159421A (en) * | 1995-11-24 | 1997-09-17 | 丸善石油化学株式会社 | Porous carbon material containing minute pores, and process for preparing the same |
| CN101066757A (en) * | 2007-05-11 | 2007-11-07 | 东华大学 | Process of preparing asphalt carbon foam material |
| JP5456392B2 (en) * | 2009-07-09 | 2014-03-26 | 国立大学法人三重大学 | Negative electrode material for lithium ion secondary battery and lithium ion secondary battery |
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN103311519A (en) * | 2012-03-07 | 2013-09-18 | 上海杉杉科技有限公司 | Composite hard carbon negative electrode material, and preparation method and application thereof |
| CN103806129A (en) * | 2014-02-19 | 2014-05-21 | 中国科学院化学研究所 | Nitrogen-doped porous carbon fiber material and preparation method and application thereof |
| CN103811737A (en) * | 2014-03-03 | 2014-05-21 | 杭州师范大学 | Preparation method of high-performance flexible lithium ion battery electrode material |
| CN103855361A (en) * | 2014-03-28 | 2014-06-11 | 清华大学 | Method for preparing nitrogen-doped porous carbon nanofiber cloth |
| CN105565297A (en) * | 2014-10-13 | 2016-05-11 | 徐海波 | Graphene quantum dot prepared from tip surface of carbon fiber through electrochemical oxidation and cutting, and preparation method thereof |
| CN106486673A (en) * | 2015-08-25 | 2017-03-08 | 神华集团有限责任公司 | Material with carbon element for lithium ion battery negative and preparation method thereof and lithium ion battery negative and lithium ion battery |
| CN106654190A (en) * | 2016-11-04 | 2017-05-10 | 华中科技大学 | One-dimensional In<2>O<3>/C fiber composite material, and preparation method and application thereof |
| CN108270007A (en) * | 2017-01-03 | 2018-07-10 | 神华集团有限责任公司 | Carbon raw material composition and its application and carbon material and its preparation method and application and negative electrode of lithium ion battery and lithium ion battery |
| CN106941167A (en) * | 2017-04-17 | 2017-07-11 | 中航锂电（洛阳）有限公司 | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113346076A (en) * | 2021-05-14 | 2021-09-03 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN113346076B (en) * | 2021-05-14 | 2023-01-24 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
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