CN110247032A - Nitrogen-doped graphene negative electrode material and preparation method thereof and lithium ion battery - Google Patents
Nitrogen-doped graphene negative electrode material and preparation method thereof and lithium ion battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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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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Abstract
This disclosure relates to a kind of nitrogen-doped graphene negative electrode material and preparation method thereof and lithium ion battery, which includes: that etching processing is carried out after mixing graphene raw material with etching agent, obtains porous graphene；Processing is doped after gained porous graphene is mixed with nitrogen-containing solvent under the conditions of closed solvent heat, obtains nitrogen-doped graphene negative electrode material.The nitrogen-doped graphene negative electrode material of method of disclosure preparation is applied to have height ratio capacity in lithium ion battery.
Description
Technical field
This disclosure relates to technical field of lithium batteries, and in particular, to a kind of nitrogen-doped graphene negative electrode material and its preparation
Method and lithium ion battery.
Background technique
With the development of new-energy automobile, hybrid vehicle (HEV), pure electric automobile (BEV) and plug-in mixing are dynamic
Power automobile (PHEV) has been to be concerned by more and more people.And in the development process of electric car, the specific capacity of power battery at
To limit the important restriction factor of Development of Electric Vehicles, thus it is electronic as being promoted to produce the power battery with height ratio capacity
Automobile course continuation mileage accelerates an important factor for Development of Electric Vehicles.In current lithium-ion-power cell produced, graphite material
Material is main negative electrode material, and theoretical specific capacity limits the promotion of battery capacity.
Graphene is by sp2The monoatomic layer ultra-thin two-dimension crystalline material that the carbon atom of hydridization is interconnected to constitute,
High specific capacity and excellent stability are shown in negative electrode material as lithium ion battery.But intrinsic graphene lacks
The marginal fold and Active site structure of lithium ion are transmitted, and N doping is carried out to graphene, graphene surface pleat can be increased
Wrinkle and defect sturcture increase the interlamellar spacing of graphene accumulation, reduce the barrier potential that lithium ion intercalation enters between graphene layer, pole
The earth promotes the capacity of lithium ion battery and high rate performance (refers to Reddy A L M, Srivastava A, Gowda S R, et
al.Synthesis of nitrogen-doped graphene films for lithium battery application
[J].Acs Nano,2010,4(11):6337-6342).However, the existence form of nitrogen is in nitrogen-doped graphene with pyridine
Three kinds of nitrogen, pyrroles's nitrogen and graphite nitrogen forms exist, and controllable nitrogen-doped graphene is rarely reported.On the skeleton of graphene, pyridine
Nitrogen and pyrroles's nitrogen can form a kind of reversible nitrogenous lithium ion compound with lithium ion, to greatly improve the reversible appearance of battery
Amount, therefore improve one of the direction that pyridine nitrogen and pyrroles's nitrogen content in graphene are nitrogen-doped graphene research.
Summary of the invention
Purpose of this disclosure is to provide a kind of nitrogen-doped graphene negative electrode material and preparation method thereof and lithium ion batteries, originally
The nitrogen-doped graphene negative electrode material of published method preparation is applied to have height ratio capacity in lithium ion battery.
To achieve the goals above, the disclosure provides a kind of preparation method of nitrogen-doped graphene negative electrode material, the preparation
Method includes:
Etching processing is carried out after graphene raw material is mixed with etching agent, obtains porous graphene；
Processing is doped after gained porous graphene is mixed with nitrogen-containing solvent under the conditions of closed solvent heat, obtains nitrogen
Doped graphene negative electrode material.
Optionally, the graphene raw material is selected from the graphene oxide of graphene and/or reduction.
Optionally, the etching agent is potassium hydroxide；The condition of the etching processing includes: that temperature is 600-800 DEG C, when
Between be 1-6 hour, the mixed weight ratio of the etching agent and graphene raw material is 1:(0.1-10).
Optionally, the nitrogen-containing solvent is selected from one of hydrazine hydrate, ammonium hydroxide, urea, acetonitrile and pyrroles or a variety of.
Optionally, it is 1 that the condition of the doping treatment, which includes: the weight ratio of the porous graphene and nitrogen-containing solvent:
(0.1-100), temperature are 150-240 DEG C, and the time is 6-48 hours.
The disclosure also provides nitrogen-doped graphene negative electrode material prepared by provided preparation method.
The disclosure also provides a kind of nitrogen-doped graphene negative electrode material, is measured using x-ray photoelectron spectroscopy, with the N doping
In graphene negative electrode material on the basis of the total weight of pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen, the content of the pyridine nitrogen is 40-50 weight
% is measured, the content of the pyrroles's nitrogen is 35-40 weight %, and the content of the graphite nitrogen is 15-25 weight %.
The disclosure also provides a kind of lithium ion battery, which includes anode, cathode, diaphragm and electrolyte, institute
Stating cathode includes nitrogen-doped graphene negative electrode material provided by the disclosure.
It further includes acetylene black and Kynoar, the nitrogen-doped graphene cathode material that the disclosure, which also provides the cathode,
The weight ratio of material, acetylene black and Kynoar is (75-85): (5-15): 10；
The positive electrode of the anode is in LiFePO4, LiMn2O4, lithium nickelate, cobalt acid lithium and nickel cobalt mangaic acid ternary lithium
It is one or more；
The electrolyte includes lithium hexafluoro phosphate and/or lithium perchlorate.
Optionally, the electrolyte includes lithium hexafluoro phosphate, ethylene carbonate and dimethyl carbonate, six in the electrolyte
The concentration of lithium fluophosphate is 0.5-2.5 mol/L, and the volume ratio of ethylene carbonate and dimethyl carbonate is 1:(0.5-2).
The disclosure carries out N doping to graphene etching and under the conditions of closed solvent heat by way of doping treatment, will
The nitrogen-doped graphene can be improved the specific capacity and efficiency of lithium ion battery as negative electrode material, to promotion electric car
Cruising ability is of great significance.
Graphene etch doping process and lithium-ion-power cell assembly technology it is simple, can mass production, obtained lithium
Ion battery has very high specific capacity.Pass through the available N doping graphite with specific nitrogenous type of such form
The lithium-ion-power cell of alkene plays exemplary role, i.e. this hair in lithium-ion-power cell materials'use and development process
Application of the bright method in modified graphene material forms nitrogen-doped graphene mainly based on pyridine nitrogen and pyrroles's nitrogen and is
The lithium-ion-power cell of negative electrode material.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is the preparation principle schematic diagram of the nitrogen-doped graphene negative electrode material based on pyridine nitrogen and pyrroles's nitrogen.
Fig. 2 is the transmission electron microscope photo of the nitrogen-doped graphene negative electrode material based on pyridine nitrogen and pyrroles's nitrogen.
Fig. 3 is the X-ray photoelectron spectroscopic analysis of the nitrogen-doped graphene negative electrode material based on pyridine nitrogen and pyrroles's nitrogen
Spectrogram (ordinate is without unit).
Fig. 4 is the performance test curve graph of half-cell provided by the embodiment of the present disclosure 1.
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched
The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
As shown in Figure 1, the disclosure provides a kind of preparation method of nitrogen-doped graphene negative electrode material, the preparation method packet
It includes:
Etching processing is carried out after graphene raw material is mixed with etching agent, obtains porous graphene；
Processing is doped after gained porous graphene is mixed with nitrogen-containing solvent under the conditions of closed solvent heat, obtains nitrogen
Doped graphene negative electrode material.
Pyridine nitrogen and pyrroles's nitrogen can form a kind of reversible nitrogenous lithium ion compound with lithium ion, can greatly improve
The reversible capacity of battery, and in actual fabrication process, nitrogen is in nitrogen-doped graphene with pyrroles's nitrogen, pyridine nitrogen and graphite nitrogen
It is random to exist.Therefore, the disclosure carries out porous activation processing to obtain porous graphene, then with nitrogenous molten to graphene first
Agent carries out N doping, and the content of pyridine nitrogen and pyrroles's nitrogen in nitrogen-doped graphene negative electrode material can be improved, obtain mainly with pyrrole
Nitrogen-doped graphene negative electrode material based on pyridine nitrogen and pyrroles's nitrogen.Using the negative electrode material as the cathode material of lithium-ion-power cell
Material carries out assembled battery, obtains having using pyridine nitrogen and pyrroles's nitrogen as the nitrogen-doped graphene lithium-ion-power cell of principal mode
Effect improves the specific capacity of battery.
According to the disclosure, graphene raw material is well-known to those skilled in the art, for example, the graphene raw material is selected from
Graphene and/or the graphene oxide of reduction, those skilled in the art can also use other graphene raw materials, and the disclosure is no longer
It repeats.The graphene oxide of reduction can restore to obtain using the graphene oxide of modified Hummers method preparation, modified
Hummers method be it is well-known to those skilled in the art, the disclosure repeats no more.
According to the disclosure, etching processing is porous for making to generate in graphene raw material, and then improves solvent heat treatment process
The efficiency of middle N doping, the etching agent can be potassium hydroxide, and the condition of the etching processing may include: that temperature is 600-
800 DEG C, the time is 1-6 hours, and the mixed weight ratio of the etching agent and graphene raw material is 1:(0.1-10).Etching agent and stone
Black alkene raw material can be mixed directly, the methods of etching agent can also be impregnated and to be loaded in graphene raw material, for example, both it is mixed
Closing step may include: to impregnate graphene raw material with certain density etching agent aqueous solution, obtain graphene and etching after dry
The mixture of agent is used for etching processing.
According to the disclosure, doping treatment is used to for nitrogen being doped into porous graphene under the conditions of closed solvent heat,
The nitrogen-containing solvent can be selected from one of hydrazine hydrate, ammonium hydroxide, urea, acetonitrile and pyrroles or a variety of, and above-mentioned material is inexpensively easy
, it is at low cost.The condition of the solvent heat treatment may include: that the weight ratio of the porous graphene and nitrogen-containing solvent is 1:
(0.1-100), temperature are 150-240 DEG C, and the time is 6-48 hours.
According to the disclosure, solvent thermal process be it is well-known to those skilled in the art, doping treatment can be in a kettle
It carries out, the material after solvent heat treatment can be with cooled to room temperature, then through the separation of solid and liquid such as centrifugation, washing and drying
Afterwards, nitrogen-doped graphene negative electrode material is obtained.
The disclosure also provides nitrogen-doped graphene negative electrode material prepared by provided preparation method.
The disclosure also provides a kind of nitrogen-doped graphene negative electrode material, is measured using x-ray photoelectron spectroscopy, with the N doping
In graphene negative electrode material on the basis of the total weight of pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen, the content of the pyridine nitrogen is 40-50 weight
% is measured, the content of the pyrroles's nitrogen is 33-40 weight %, and the content of the graphite nitrogen is 15-25 weight %.What the disclosure provided
Nitrogen-doped graphene negative electrode material has high pyridine nitrogen content and pyrroles's nitrogen content, low graphite nitrogen content.
The disclosure also provides a kind of lithium ion battery, which includes anode, cathode, diaphragm and electrolyte, institute
Stating cathode includes nitrogen-doped graphene negative electrode material provided by the disclosure.
According to the disclosure, in lithium ion battery other than the nitrogen-doped graphene negative electrode material provided by the disclosure,
Its component can use component well-known to those skilled in the art and material, for example, the cathode can also include acetylene
The weight ratio of black and Kynoar, the nitrogen-doped graphene negative electrode material, acetylene black and Kynoar is (75-85):
(5-15): 10；The positive electrode of the anode can be selected from LiFePO4, LiMn2O4, lithium nickelate, cobalt acid lithium and nickel cobalt mangaic acid three
One of first lithium is a variety of.The electrolyte may include lithium hexafluoro phosphate and/or lithium perchlorate, such as the electrolyte can
To include lithium hexafluoro phosphate, ethylene carbonate and dimethyl carbonate, the concentration of lithium hexafluoro phosphate can be in the electrolyte
The volume ratio of 0.5-2.5 mol/L, ethylene carbonate and dimethyl carbonate can be 1:(0.5-2).
Carry out the further disclosure below by embodiment, but therefore the disclosure is not any way limited.
In the disclosure unless otherwise specified, agents useful for same is that commercially available income analysis is pure, and different reagents do not influence using effect
Fruit.
The graphene of the disclosure is to be commercially available, and the graphene oxide of reduction is the oxidation stone of modified Hummers method preparation
Black alkene restores to obtain.
The step of transmission electron microscope (TEM) carries out morphology analysis to obtained nitrogen-doped graphene negative electrode material is such as
Under: it takes micro-example dispersion in ethanol, uniform suspension is dispersed to sample ultrasonic using cell disruptor, is inhaled with liquid-transfering gun
It takes a small amount of dispersant liquid drop in micro-grid, is toasted with infrared lamp, carry out TEM test after ethyl alcohol volatilization completely.
The step of x-ray photoelectron spectroscopy (XPS) analyzes the nitrogenous type and content of nitrogen-doped graphene negative electrode material
As follows: then first 60 DEG C of bakings water removal in 24 hours in vacuum drying oven by nitrogen-doped graphene negative electrode material carries out XPS test.It surveys
Strip part: excitaton source MgK α (1253.6eV), power 450W, vacuum degree 10-8~10-9Torr.Used instrument model is
The PHI1600X photoelectron spectrograph of PERKIN ELMZR company.Pyrroles's nitrogen, pyridine nitrogen and graphite nitrogen corresponding 398,400 and 402
The characteristic peak at place calculates the relative amount of pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen by the relative scale of characteristic peak peak area.
Embodiment 1
Processing 2 hours is performed etching at 600 DEG C after the graphene that weight ratio is 1:5 is mixed in tube furnace with KOH,
Obtaining surface has porous and defect sturcture porous graphene.
It is put into reaction kettle after gained porous graphene is mixed with urea according to weight ratio 1:10, in closed self-generated pressure
Under reacted 24 hours at 150 DEG C, then cooled to room temperature after reaction is centrifuged, is washed and is dried, obtains N doping
Graphene negative electrode material, transmission electron microscope photo are shown in that Fig. 2, X-ray photoelectron spectroscopic analysis spectrogram are shown in Fig. 3.Through detecting, material
The content of pyridine nitrogen is 48 weight % in material, and the content of pyrroles's nitrogen is 36 weight %, and graphite nitrogen content is 16 weight %.
Nitrogen-doped graphene negative electrode material, acetylene black and Kynoar are mixed according to the ratio of weight ratio 80:10:10
It closes, wet grinding is then carried out in N-Methyl pyrrolidone (NMP) into slurry, slurry is equably coated on copper foil, is put
It is placed in convection oven and is dried 2 hours at 55 DEG C, then be placed in a vacuum drying oven drying 24 hours, obtain cathode.
Using the ethylene carbonate and dimethyl carbonate solution of 1 mol/L lithium hexafluoro phosphate as electrolyte, ethylene carbonate
The volume ratio of ester and dimethyl carbonate is 1:1.
Anode, cathode, diaphragm, electrolyte and battery case are carried out to the assembling of half-cell in the glove box full of argon gas.
When assembly, reference is metal lithium sheet to electrode, then diaphragm model Celgrad3500 carries out electrochemical property test, is tested
Current density is 100mAh g-1, charge and discharge cycles circle number is 1-100 circle, and performance test curve graph is shown in Fig. 4.
From fig. 4, it can be seen that battery specific capacity is 1100mAh/g after circulation 100 times.
Embodiment 2
Substantially the same manner as Example 1, the difference is that the temperature of etching processing is 800 DEG C, the time is 1 hour, etching
The mixed weight of agent and graphene raw material ratio is 1:10；Nitrogen-containing solvent used in doping treatment is hydrazine hydrate, porous graphene and water
Conjunction hydrazine weight ratio is 1:50, and temperature is 240 DEG C, and the time is 12 hours.Pyridine nitrogen in gained nitrogen-doped graphene negative electrode material
Content is 45 weight %, and the content of pyrroles's nitrogen is 34 weight %, and graphite nitrogen content is 21 weight %.
Nitrogen-doped graphene negative electrode material obtained by the present embodiment is assembled into battery and carries out electrochemical property test, circulation
After 100 times, battery specific capacity is 1000mAh/g.
Embodiment 3
Substantially the same manner as Example 1, the difference is that the temperature of etching processing is 700 DEG C, the time is 6 hours, etching
The mixed weight of agent and graphene raw material ratio is 1:10；Nitrogen-containing solvent used in doping treatment is acetonitrile, porous graphene and urea
Weight ratio is 1:10, and temperature is 200 DEG C, and the time is 24 hours.The content of pyridine nitrogen in gained nitrogen-doped graphene negative electrode material
For 46 weight %, the content of pyrroles's nitrogen is 38 weight %, and graphite nitrogen content is 16 weight %.
Nitrogen-doped graphene negative electrode material obtained by the present embodiment is assembled into battery and carries out electrochemical property test, circulation
After 100 times, battery specific capacity is 1100mAh/g.
Embodiment 4
It is substantially the same manner as Example 1, the difference is that graphene raw material used is the graphene oxide of reduction.Gained nitrogen
The content of pyridine nitrogen is 40 weight % in doped graphene negative electrode material, and the content of pyrroles's nitrogen is 36 weight %, graphite nitrogen content
For 24 weight %.
Nitrogen-doped graphene negative electrode material obtained by the present embodiment is assembled into battery and carries out electrochemical property test, circulation
After 100 times, battery specific capacity is 900mAh/g.
Comparative example 1
Nitrogen-doped graphene cathode material preparation method are as follows: after mixing by urea and graphene, under protection of argon gas
It is reacted 5 hours at 900 DEG C.The content of pyridine nitrogen is 40 weight % in gained nitrogen-doped graphene negative electrode material, pyrroles's nitrogen
Content is 28 weight %, and graphite nitrogen content is 32 weight %.
Nitrogen-doped graphene negative electrode material obtained by this comparative example is assembled into battery and carries out electrochemical property test, circulation
After 100 times, battery specific capacity is 700mAh/g.
Comparative example 2
It is substantially the same manner as Example 1, the difference is that graphene without etching processing, is directly doped processing,
The content of pyridine nitrogen is 32 weight % in gained nitrogen-doped graphene negative electrode material, and the content of pyrroles's nitrogen is 28 weight %, graphite
Nitrogen content is 40 weight %.
Nitrogen-doped graphene negative electrode material obtained by this comparative example is assembled into battery and carries out electrochemical property test, circulation
After 100 times, battery specific capacity is 650mAh/g.
Comparative example 3
It is substantially the same manner as Example 1, the difference is that the preparation method of nitrogen-doped graphene negative electrode material is first mixed
Reason is lived together, carries out etching processing afterwards, method particularly includes:
Be put into reaction kettle after gained graphene is mixed with urea according to weight ratio 1:10, under closed self-generated pressure in
It is reacted 24 hours at 150 DEG C, then cooled to room temperature after reaction is centrifuged, is washed and is dried, then by gained graphite
Alkene is that processing 2 hours is performed etching at 600 DEG C after 1:5 is mixed in tube furnace with KOH according to weight ratio, obtains N doping stone
Black alkene negative electrode material.Through detecting, the content of pyridine nitrogen is 40 weight % in material, and the content of pyrroles's nitrogen is 15 weight %, graphite
Nitrogen content is 45 weight %.
Nitrogen-doped graphene negative electrode material obtained by this comparative example is assembled into battery and carries out electrochemical property test, circulation
After 100 times, battery specific capacity is 700mAh/g.
Comparative example 4
It is substantially the same manner as Example 1, the difference is that graphene is without etching processing and adulterates nitrogen, directly as negative
Pole material prepares battery.
Nitrogen-doped graphene negative electrode material obtained by this comparative example is assembled into battery and carries out electrochemical property test, circulation
After 100 times, battery specific capacity is 400mAh//g.
From embodiment and comparative example as can be seen that using disclosed method by preparation based on pyridine nitrogen and pyrroles's nitrogen
Nitrogen-doped graphene be lithium ion battery negative electrode material, carry out electrochemical property test after being assembled into half-cell, obtain
Lithium-ion-power cell has height ratio capacity and efficiency.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (10)
1. a kind of preparation method of nitrogen-doped graphene negative electrode material, the preparation method include:
Etching processing is carried out after graphene raw material is mixed with etching agent, obtains porous graphene；
Processing is doped after gained porous graphene is mixed with nitrogen-containing solvent under the conditions of closed solvent heat, obtains N doping
Graphene negative electrode material.
2. preparation method according to claim 1, wherein the graphene raw material is selected from the oxygen of graphene and/or reduction
Graphite alkene.
3. preparation method according to claim 1, wherein the etching agent is potassium hydroxide；
The condition of the etching processing includes: that temperature is 600-800 DEG C, and the time is 1-6 hours, and the etching agent and graphene are former
The mixed weight ratio of material is 1:(0.1-10).
4. preparation method according to claim 1, wherein the nitrogen-containing solvent is selected from hydrazine hydrate, ammonium hydroxide, urea, acetonitrile
With one of pyrroles or a variety of.
5. preparation method according to claim 1, wherein the condition of the doping treatment includes: the porous graphene
Weight ratio with nitrogen-containing solvent is 1:(0.1-100), temperature is 150-240 DEG C, and the time is 6-48 hours.
6. nitrogen-doped graphene negative electrode material prepared by preparation method described in any one of claim 1-5.
7. a kind of nitrogen-doped graphene negative electrode material, is measured using x-ray photoelectron spectroscopy, with the nitrogen-doped graphene negative electrode material
On the basis of the total weight of middle pyridine nitrogen, pyrroles's nitrogen and graphite nitrogen, the content of the pyridine nitrogen is 40-50 weight %, the pyrroles
The content of nitrogen is 33-40 weight %, and the content of the graphite nitrogen is 15-25 weight %.
8. a kind of lithium ion battery, which includes anode, cathode, diaphragm and electrolyte, and the cathode includes right
It is required that nitrogen-doped graphene negative electrode material described in 6 or 7.
9. lithium ion battery according to claim 8, wherein the cathode further includes acetylene black and Kynoar, institute
The weight ratio for stating nitrogen-doped graphene negative electrode material, acetylene black and Kynoar is (75-85): (5-15): 10；
The positive electrode of the anode in LiFePO4, LiMn2O4, lithium nickelate, cobalt acid lithium and nickel cobalt mangaic acid ternary lithium one
Kind is a variety of；
The electrolyte includes lithium hexafluoro phosphate and/or lithium perchlorate.
10. lithium ion battery according to claim 8, wherein the electrolyte includes lithium hexafluoro phosphate, ethylene carbonate
And dimethyl carbonate, the concentration of lithium hexafluoro phosphate is 0.5-2.5 mol/L, ethylene carbonate and carbonic acid two in the electrolyte
The volume ratio of methyl esters is 1:(0.5-2).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130042845A (en) * | 2011-10-19 | 2013-04-29 | 한국과학기술원 | Method for adsorbtion of various biomaterials to chemically modified graphene |
| CN104649253A (en) * | 2013-11-18 | 2015-05-27 | 国家纳米科学中心 | Preparing methods of porous graphene and porous graphene film |
| CN105810945A (en) * | 2016-05-26 | 2016-07-27 | 江苏深苏电子科技有限公司 | Preparation method of lithium ion battery cathode material nitrogen-doped three-dimensional porous graphene |
| CN107827103A (en) * | 2017-12-07 | 2018-03-23 | 太原理工大学 | The preparation method and applications of N doping porous graphene |
| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
-
2019
- 2019-05-28 CN CN201910452744.XA patent/CN110247032B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130042845A (en) * | 2011-10-19 | 2013-04-29 | 한국과학기술원 | Method for adsorbtion of various biomaterials to chemically modified graphene |
| CN104649253A (en) * | 2013-11-18 | 2015-05-27 | 国家纳米科学中心 | Preparing methods of porous graphene and porous graphene film |
| CN105810945A (en) * | 2016-05-26 | 2016-07-27 | 江苏深苏电子科技有限公司 | Preparation method of lithium ion battery cathode material nitrogen-doped three-dimensional porous graphene |
| CN107827103A (en) * | 2017-12-07 | 2018-03-23 | 太原理工大学 | The preparation method and applications of N doping porous graphene |
| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
Non-Patent Citations (1)
| Title |
|---|
| YANWU ZHU等: ""Carbon-Based Supercapacitors Produced by Activation of Graphene"", 《SCIENCE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111584866A (en) * | 2020-05-27 | 2020-08-25 | 安徽科达新材料有限公司 | Preparation method of high-rate artificial graphite negative electrode material |
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