CN110980720B - Nitrogen-doped graphite material and preparation method and application thereof - Google Patents
Nitrogen-doped graphite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen-doped graphite material, a preparation method and application thereof, wherein the nitrogen-doped graphite material comprises carbon elements, nitrogen elements and oxygen elements, the ratio of the number of nitrogen atoms to the number of carbon atoms is 2.5-5.0%, the nitrogen-doped graphite material is of a graphite-like structure, and part of the nitrogen atoms and the carbon atoms form graphite type nitrogen, pyridine type nitrogen and pyrrole type nitrogen. The preparation method of the nitrogen-doped graphite material comprises the following steps: s10, mixing a non-graphite carbon source raw material, a nitrogen source raw material and water in proportion to form a solution; s20 reacting at low temperature to form a nitrogen-containing precursor; s30 high-temperature reduction calcination of the nitrogen-containing precursor. The medium-nitrogen-doped graphite material has good conductivity and excellent lithium ion releasing/embedding performance, is expressed by high reversible capacity, excellent rate capability and cycle performance, has wide raw material source and good product consistency in the preparation method, and can realize large-scale production.
Description
Technical Field
The invention relates to a preparation technology of a lithium battery material, in particular to a nitrogen-doped graphite material and a preparation method and application thereof.
Background
The lithium ion battery has excellent performance and is widely applied to various fields, and the main components of the lithium ion battery are a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode material determines the energy density of the lithium ion battery to a great extent. From the commercialization of lithium ion batteries to the present, graphite is the most mature and widely used negative electrode material. The graphite has a six-membered ring carbon network layered structure, the carbon carbons are hybridized by SP2, and the layers are connected by molecular acting force. The specific capacity of the graphite cathode material is low, the maximum theoretical capacity is 372mAh/g, and the defect of large irreversible capacity exists for the first time, so that the reversible specific capacity is only 260mAh/g, and the irreversible specific capacity is more than 100 mAh/g. Therefore, the graphite negative electrode material cannot meet the requirements of people on high-capacity lithium ion batteries.
Currently, researchers mainly use methods such as surface treatment, surface coating, element doping and the like to perform modification research on the graphite cathode so as to improve the structural defects of the graphite cathode and improve the performance of the battery.
The invention patent application CN108706578A discloses a nitrogen-doped graphene, a preparation method thereof and a capacitor, wherein the scheme is to ball mill a mixture of graphene and a nitrogen source; and calcining the product obtained by ball milling to obtain the nitrogen-doped graphene. According to the method, graphene is used as a raw material, and the cost of the scheme is high due to the fact that the price of the existing graphene is high. In addition, the nitrogen-doped graphene prepared by the method is applied to the field of capacitors, and does not relate to the field of lithium ion batteries, the fields are different, and the technical points of the materials are different.
Disclosure of Invention
The invention aims to solve the problems of low reversible specific capacity and poor cycle performance of the conventional graphite cathode material of the lithium ion battery, and provides a nitrogen-doped graphite material. Specifically, a nitrogen source material and a non-graphite carbon source material are used as raw materials, a high-nitrogen-content precursor is formed through a low-temperature reaction, and then the nitrogen-doped graphite cathode material is prepared through high-temperature calcination reduction. The method is an in-situ reaction method, pyridine type nitrogen (pyridine N) and pyrrole type nitrogen (Pyrrolic N) with high proportion can be formed, and the nitrogen-doped graphite is used as a negative electrode material, so that the conductivity and the lithium removal/insertion performance of the graphite can be obviously improved. Meanwhile, compared with the traditional surface modification, surface modification and other technologies, the method has the advantages of wide raw material source, low cost, good product consistency and realization of large-scale production.
In the present invention, Graphitic nitrogen (graphite N) refers to a nitrogen atom in which three carbon atoms are connected in a hexagonal plane; pyridine nitrogen (pyridine N) refers to a nitrogen atom attached to two carbons at the edge of the plane of a hexagonal network, which can provide one electron and a lone pair of electrons to a conjugated pi bond; pyrrole nitrogen (Pyrrolic N) refers to a nitrogen atom bearing two electrons and conjugated with a π bond.
The preparation method is different from the traditional method which takes graphite as a raw material in the aspect of preparation idea, for example, in the invention patent application CN108706578A, graphene is adopted as a raw material, nitrogen doping is realized by combining with calcination of a nitrogen source, the scheme adopts low-temperature reaction and high-temperature calcination reduction of a carbon source and a nitrogen source to prepare the graphite-like material, and simultaneously realizes in-situ doping of nitrogen to form different types of nitrogen-doped atoms (graphite-type nitrogen, pyridine-type nitrogen and pyrrole-type nitrogen), and the nitrogen source not only has the function of forming the graphite-like material by low-temperature reaction with the carbon source, but also serves as a nitrogen doping source.
The ratio of the number of nitrogen atoms to the number of carbon atoms in the nitrogen-doped graphite material is 2.5-5.0%, and the nitrogen atoms and the carbon atoms form graphite type nitrogen (graphite N), pyridine type nitrogen (pyridine N) and pyrrole type nitrogen (Pyrrolic N). Wherein the atomic number of the pyridine type nitrogen (pyridine N) and the pyrrole type nitrogen (Pyrrolic N) is 65% to 85% of the nitrogen atom number. Wherein the nitrogen-doped graphite material contains oxygen, and the ratio of the number of oxygen atoms to the number of carbon atoms is 2.0% to 4.0%.
The invention also provides a preparation method of the nitrogen-doped graphite material, which comprises the following steps: s10, mixing a non-graphite carbon source raw material, a nitrogen source raw material and water in proportion to form a solution; s20 reacting at low temperature to form a nitrogen-containing precursor; s30 high-temperature reduction calcination of the nitrogen-containing precursor.
Wherein, S10 adopts non-graphite carbon source, such as glucose, citric acid and sucrose, which has wide source and low cost. The nitrogen source raw material is one or a combination of more of glycine, urea and alanine, and the material has the advantages of simple structure, high nitrogen content, high doping efficiency and low cost. The amount of the deionized water is enough to just dissolve the carbon source raw material and the nitrogen source raw material, the reaction is not uniform due to the excessively low amount of the deionized water, the heating time is prolonged due to the excessively high amount of the deionized water, and the reaction efficiency is not improved.
S20 low-temperature reaction to form nitrogen-containing precursor, which mainly generates thermal decomposition reaction of carbon source raw material and nitrogen source raw material to generate carbon atom recombination and nitrogen atom implantation doping. The low-temperature heating temperature is 160-280 ℃, the heating time is 5-20 minutes, or the time for volatilizing the solution and forming the solid is taken as the standard. Temperatures above 280 ℃ can cause charring of the material and formation of nitride gas from nitrogen atoms, failing to form graphite-like materials and failing to achieve nitrogen doping.
S30 high-temperature reduction calcination of the nitrogen-containing precursor, wherein the oxygen element is contained in the product under the reducing atmosphere because oxygen is adsorbed on the surface of the material. The ratio of the number of oxygen atoms to the number of carbon atoms in the product is 2.0-4.0%, and the oxygen atoms are mainly from the surface adsorption of oxygen, so that the material performance is not adversely affected.
The specific scheme is as follows:
a nitrogen-doped graphite-like material comprising a carbon element, a nitrogen element and an oxygen element, wherein the ratio of the number of nitrogen atoms to the number of carbon atoms is 2.5% to 5.0%, the nitrogen-doped graphite-like material is of a graphite-like structure, and part of the nitrogen atoms and the carbon atoms form graphite-type nitrogen, pyridine-type nitrogen and pyrrole-type nitrogen.
Further, the atomic number of the pyridine type nitrogen and the pyrrole type nitrogen accounts for 65% to 85% of the nitrogen atom number;
optionally, the ratio of the number of nitrogen atoms to the number of carbon atoms is from 3.8% to 4.2%.
Further, the ratio of the number of oxygen atoms to the number of carbon atoms is 2.0% to 4.0%;
optionally, the atomic number of the pyridine type nitrogen and the pyrrole type nitrogen is 72% to 84% of the number of nitrogen atoms.
The invention also provides a preparation method of the nitrogen-doped graphite material, which comprises the following steps:
step S10, mixing non-graphite carbon source raw materials, nitrogen source raw materials and deionized water into a solution; wherein the carbon source raw material and the nitrogen source raw material are analytically pure, and the deionized water is used for just dissolving the carbon source raw material and the nitrogen source raw material;
step S20, putting the mixed solution into heating equipment for low-temperature heating, and reacting to form a nitrogen-containing precursor; wherein the low-temperature heating temperature is 160-280 ℃;
and step S30, putting the nitrogen-containing precursor into an atmosphere heating furnace for high-temperature reduction calcination treatment to form the nitrogen-doped graphite material.
Further, in the step S10, the mass ratio of the non-graphitic carbon source material to the nitrogen source material is 1/2 to 2; optionally, the carbon source raw material is one or more of glucose, citric acid and sucrose;
optionally, the nitrogen source raw material is one or more of glycine, urea and alanine.
Further, the heating time in the step S20 is 5 to 20 minutes, or the time for the solution to volatilize and form a solid is taken as a standard; wherein, the heating is one of muffle furnace heating, microwave heating or infrared heating;
optionally, the temperature of the calcination treatment in the step S30 is 700 ℃ to 1200 ℃, and the calcination time is 1 hour to 2 hours; optionally, the reductive calcination is carried out by passing a reducing gas through the heating process, wherein the gas flow rate is 500 ml/min to 1000 ml/min, and the reducing gas is hydrogen or a hydrogen-nitrogen mixed gas.
The invention also protects the nitrogen-doped graphite material prepared by the preparation method of the nitrogen-doped graphite material, and the nitrogen-doped graphite material has a graphite-like structure, and graphite type nitrogen, pyridine type nitrogen and pyrrole type nitrogen are formed by partial nitrogen atoms and carbon atoms.
The invention also protects the application of the nitrogen-doped graphite material, and the nitrogen-doped graphite material is used as a lithium ion battery cathode material.
The invention also provides a lithium ion battery cathode material which comprises an active material, a binder, a solvent and a conductive material, wherein the active material is the nitrogen-doped graphite-like material.
The invention also provides a lithium ion battery, which comprises a positive electrode material, a negative electrode material and an electrolyte, wherein the negative electrode material is the lithium ion battery negative electrode material.
Has the advantages that:
the medium-nitrogen-doped graphite-like material has a graphite-like structure, contains rich nitrogen elements, has good conductivity and excellent lithium ion removal/insertion performance, and is high in reversible capacity, excellent in rate capability and cycle performance.
The invention further provides a preparation method of the nitrogen-doped graphite cathode material, which is characterized in that a precursor with high nitrogen content is synthesized through low-temperature reaction, and then the nitrogen-doped graphite cathode material is prepared through high-temperature calcination and reduction.
Furthermore, the preparation process is simple, the cost is low, the graphite-like material is synthesized in the preparation process, and the modification is carried out without using graphite as a raw material, which is obviously different from the traditional graphite nitrogen doping modification method.
Finally, after a large amount of nitrogen is doped, the nitrogen atoms and the carbon atoms form graphite type nitrogen (graphite N), pyridine type nitrogen (pyridine N) and pyrrole type nitrogen (Pyrrolic N), so that the conductivity and the lithium release/insertion performance of the graphite are obviously improved, and the graphite has high reversible capacity, excellent rate capability and cycle performance when being used as a lithium ion battery cathode material. Compared with the traditional surface modification, surface modification and other technologies, the method has the advantages of wide raw material source, good product consistency and realization of large-scale production.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
Fig. 1 is an SEM image of the nitrogen-doped graphite-like material prepared in example 1.
Fig. 2 is an SEM image of the nitrogen-doped graphite-like material prepared in example 2.
Fig. 3 is an SEM image of the nitrogen-doped graphite-like material prepared in example 3.
Fig. 4 is a graph of rate capability of nitrogen-doped graphite-like negative electrode materials prepared in examples 1-3.
Fig. 5 is a graph of the cycling performance of the nitrogen-doped graphite-like negative electrode materials prepared in examples 1-3 at a current density of 1C.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
35 grams of carbon source material (30 grams citric acid +5 grams glucose), 75 grams of nitrogen source material (20 grams glycine +55 grams urea) and 20 milliliters of deionized water were mixed to form a solution. And then putting the solution into a muffle furnace, and heating for 5 minutes at 260 ℃ to obtain the nitrogen-containing precursor. And then, placing the nitrogen-containing precursor in an atmosphere heating furnace, preserving heat for 1 hour at 1000 ℃ for reduction calcination, cooling to room temperature along with the furnace after the reduction calcination, and carrying out the reduction calcination process of the nitrogen-containing precursor, including heating, preserving heat and cooling, always keeping the flowing hydrogen gas introduced, and keeping the flow at 500 ml/min. And obtaining the nitrogen-doped graphite material after the temperature reduction is finished.
The SEM micrograph of the nitrogen-doped graphite-like material prepared in this example is shown in fig. 1. The ratio of the number of nitrogen atoms to the number of carbon atoms in the nitrogen-doped graphite material prepared in this example was 4.2%, the number of atoms of pyridine nitrogen (pyridine N) and pyrrole nitrogen (pyrolic N) was 84% of the number of nitrogen atoms, and the ratio of the number of oxygen atoms to the number of carbon atoms was 2.1%.
Example 2
70 grams of carbon source material (20 grams glucose +80 grams citric acid), 35 grams of nitrogen source material (10 grams glycine +25 grams urea) and 20 milliliters deionized water were mixed to form a solution. And then putting the solution into a muffle furnace, and heating for 10 minutes at 230 ℃ to obtain the nitrogen-containing precursor. And then, the nitrogen-containing precursor is placed in an atmosphere heating furnace, heat preservation is carried out for 1.5 hours at 800 ℃ for reduction calcination, the temperature is reduced to room temperature along with the furnace after the reduction calcination, and the nitrogen-containing precursor is subjected to reduction calcination, wherein the reduction calcination process comprises heating, heat preservation and cooling, flowing hydrogen is always kept to be introduced, and the flow rate is kept at 500 ml/min. And obtaining the nitrogen-doped graphite material after the temperature reduction is finished.
The SEM micrograph of the nitrogen-doped graphite-like material prepared in this example is shown in fig. 2. The nitrogen-doped graphite material prepared in this example had a ratio of the number of nitrogen atoms to the number of carbon atoms of 3.8%, the number of atoms of pyridine nitrogen (pyridine N) and pyrrole nitrogen (pyrolic N) was 72% of the number of nitrogen atoms, and the ratio of the number of oxygen atoms to the number of carbon atoms was 3.6%.
Example 3
50 grams of carbon source material (40 grams citric acid +10 grams sucrose), 50 grams of nitrogen source material (20 grams alanine +30 grams urea) and 15 milliliters deionized water were mixed to form a solution. And then putting the solution into a muffle furnace, and heating for 15 minutes at 200 ℃ to obtain the nitrogen-containing precursor. And then, placing the nitrogen-containing precursor in an atmosphere heating furnace, preserving heat for 1 hour at 900 ℃ for reduction calcination, cooling to room temperature along with the furnace after the reduction calcination, and carrying out the reduction calcination process of the nitrogen-containing precursor, including heating, preserving heat and cooling, always keeping the flowing hydrogen gas introduced, and keeping the flow at 500 ml/min. And obtaining the nitrogen-doped graphite material after the temperature reduction is finished.
The SEM micrograph of the nitrogen-doped graphite-like material prepared in this example is shown in fig. 3. The nitrogen-doped graphite material prepared in this example had a ratio of the number of nitrogen atoms to the number of carbon atoms of 4.9%, the number of atoms of pyridine nitrogen (pyridine N) and pyrrole nitrogen (pyrolic N) was 77% of the number of nitrogen atoms, and the ratio of the number of oxygen atoms to the number of carbon atoms was 3.8%.
Example 4
75 grams of carbon source material (30 grams citric acid +35 grams glucose), 35 grams of nitrogen source material (20 grams glycine +15 grams urea) and 20 milliliters of deionized water were mixed to form a solution. And then putting the solution into a muffle furnace, and heating for 5 minutes at 280 ℃ to obtain the nitrogen-containing precursor. And then, placing the nitrogen-containing precursor in an atmosphere heating furnace, preserving heat for 1 hour at 1200 ℃ for reduction calcination, cooling to room temperature along with the furnace after the reduction calcination, and carrying out the reduction calcination process of the nitrogen-containing precursor, including heating, preserving heat and cooling, always keeping the flowing hydrogen gas introduced, and keeping the flow at 1000 ml/min. And obtaining the nitrogen-doped graphite material after the temperature reduction is finished.
Example 5
50 grams of carbon source material (30 grams citric acid +20 grams glucose), 50 grams of nitrogen source material (20 grams alanine +20 grams urea) and 20 milliliters of deionized water were mixed to form a solution. And then putting the solution into a muffle furnace, and heating for 15 minutes at 240 ℃ to obtain the nitrogen-containing precursor. And then, placing the nitrogen-containing precursor in an atmosphere heating furnace, preserving heat for 1 hour at 1100 ℃ for reduction calcination, cooling to room temperature along with the furnace after the reduction calcination, and carrying out the reduction calcination process of the nitrogen-containing precursor, including heating, preserving heat and cooling, always keeping the flowing hydrogen gas introduced, and keeping the flow at 800 ml/min. And obtaining the nitrogen-doped graphite material after the temperature reduction is finished.
Example 6
35 grams of carbon source material (30 grams citric acid +5 grams glucose), 75 grams of nitrogen source material (20 grams glycine +55 grams urea) and 20 milliliters of deionized water were mixed to form a solution. And then putting the solution into a muffle furnace, and heating for 20 minutes at 160 ℃ to obtain the nitrogen-containing precursor. And then, placing the nitrogen-containing precursor in an atmosphere heating furnace, preserving heat for 2 hours at 700 ℃ for reduction calcination, cooling to room temperature along with the furnace after the reduction calcination, and carrying out the reduction calcination process of the nitrogen-containing precursor, including heating, preserving heat and cooling, always keeping the flowing hydrogen gas introduced, and keeping the flow at 500 ml/min. And obtaining the nitrogen-doped graphite material after the temperature reduction is finished.
Example 7
35 grams of carbon source material (30 grams citric acid +5 grams glucose), 75 grams of nitrogen source material (20 grams glycine +55 grams urea) and 20 milliliters of deionized water were mixed to form a solution. And then putting the solution into a muffle furnace, and heating for 5 minutes at 200 ℃ to obtain the nitrogen-containing precursor. And then, placing the nitrogen-containing precursor in an atmosphere heating furnace, preserving heat for 1 hour at 900 ℃ for reduction calcination, cooling to room temperature along with the furnace after the reduction calcination, and carrying out the reduction calcination process of the nitrogen-containing precursor, including heating, preserving heat and cooling, always keeping the flowing hydrogen gas introduced, and keeping the flow at 500 ml/min. And obtaining the nitrogen-doped graphite material after the temperature reduction is finished.
Performance testing
The nitrogen-doped graphite-like materials synthesized in examples 1 to 3 were used as negative electrode materials. According to a formula of 94: 5: 1: the nitrogen-doped graphite material, polyvinylidene fluoride (PVDV) binder, conductive carbon black (Super P) and conductive graphite (KS-6) were weighed at a mass ratio of 0.2, and N-methylpyrrolidone (NMP) was used as a solvent, mixed and ball-milled for 3 hours to form a slurry. The slurry was uniformly coated on a copper foil and vacuum dried at 85 ℃ for 12 hours. Taking a metal lithium sheet as a counter electrode, Celgard2000 as a diaphragm, 1M LiPF6 as an electrolyte, and a solvent with a volume fraction of 1: 1: 1, mixing three components of EC, DEC and DMC, assembling a CR2032 button cell in an anhydrous glove box in an argon atmosphere, and standing and aging for 24 hours.
Fig. 4 is a graph showing rate capability of the nitrogen-doped graphite-based negative electrode materials prepared in examples 1 to 3. Fig. 5 shows the cycle performance of the nitrogen-doped graphite-like negative electrode materials prepared in examples 1 to 3 at a current density of 1C. Tests show that under the condition of 0.1C, the specific capacities of the nitrogen-doped graphite anode materials synthesized in the embodiment 1, the embodiment 2 and the embodiment 3 respectively reach 530mAh g-1, 425mAh g-1 and 382 mAh g-1, and the coulomb efficiencies of the three materials are all about 95%. By comparison, the specific capacity of example 1 is 56.8% higher than that of commercial graphite. The three samples of the embodiment have high stability under 150 cycles of large current (1C), and the coulomb efficiency of the three samples reaches about 99 percent.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A preparation method of a nitrogen-doped graphite material is characterized by comprising the following steps: the method comprises the following steps:
step S10, mixing non-graphite carbon source raw materials, nitrogen source raw materials and deionized water into a solution; wherein the carbon source raw material and the nitrogen source raw material are in analytical pure specifications, the nitrogen source raw material is one or a combination of glycine and alanine, and the deionized water is used for just dissolving the carbon source raw material and the nitrogen source raw material;
step S20, putting the mixed solution into heating equipment for low-temperature heating, and reacting to form a nitrogen-containing precursor; wherein the low-temperature heating temperature is 160-280 ℃;
and step S30, putting the nitrogen-containing precursor into an atmosphere heating furnace for high-temperature reduction calcination treatment to form the nitrogen-doped graphite material.
2. The method for preparing the nitrogen-doped graphite-like material according to claim 1, wherein: in step S10, the mass ratio of the non-graphitic carbon source material to the nitrogen source material is 1/2 to 2.
3. The method for preparing the nitrogen-doped graphite-like material according to claim 1, wherein: the carbon source raw material is one or a combination of more of glucose, citric acid and sucrose.
4. The method for preparing the nitrogen-doped graphite-like material according to claim 1, wherein: the heating time in the step S20 is 5-20 minutes; wherein, the heating is one of muffle furnace heating, microwave heating or infrared heating.
5. The method for preparing the nitrogen-doped graphite-like material according to claim 1, wherein: the heating time in the step S20 is based on the time for the solution to volatilize and form a solid.
6. The method for preparing the nitrogen-doped graphite-like material according to claim 1, wherein: the temperature of the calcination treatment in the step S30 is 700 to 1200 ℃, and the calcination time is 1 to 2 hours.
7. The method for preparing the nitrogen-doped graphite-like material according to claim 1, wherein: the reduction calcination is carried out by passing reducing gas in the heating process, the gas flow is 500 ml/min to 1000 ml/min, and the reducing gas is hydrogen or hydrogen-nitrogen mixed gas.
8. The nitrogen-doped graphite-like material prepared by the method for preparing a nitrogen-doped graphite-like material according to any one of claims 1 to 7, which has a graphite-like structure, wherein part of nitrogen atoms and carbon atoms form graphite type nitrogen, pyridine type nitrogen and pyrrole type nitrogen, and the nitrogen-doped graphite-like material comprises carbon elements, nitrogen elements and oxygen elements, wherein the ratio of the number of nitrogen atoms to the number of carbon atoms is 2.5% to 5.0%, and the number of atoms of pyridine type nitrogen and pyrrole type nitrogen accounts for 65% to 85% of the number of nitrogen atoms.
9. Use of the nitrogen-doped graphite-like material according to claim 8 as a negative electrode material for lithium ion batteries.
10. The lithium ion battery negative electrode material comprises an active material, a binder, a solvent and a conductive material, and is characterized in that: the active material is the nitrogen-doped graphite-like material of claim 8.
11. A lithium ion battery comprises a positive electrode material, a negative electrode material and an electrolyte, and is characterized in that: the negative electrode material adopts the negative electrode material of the lithium ion battery of claim 10.
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| Microwave growth and tunable photoluminescence of nitrogen-doped graphene and carbon nitride quantum dots;Gu siyong et al.;《Journal of Materials Chemistry C》;20190514;实验部分第1-2段 * |
| Nitrogen-doped porous carbon derived from citric acid and urea with outstanding supercapacitance performance;Jian Tan et al.;《Electrochimica Acta》;20150805;第178卷;全文 * |
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