CN108376767A - A kind of red phosphorus/nitrogen-doped graphene composite negative pole material and its preparation method and application - Google Patents
A kind of red phosphorus/nitrogen-doped graphene composite negative pole material and its preparation method and application Download PDFInfo
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- CN108376767A CN108376767A CN201810069146.XA CN201810069146A CN108376767A CN 108376767 A CN108376767 A CN 108376767A CN 201810069146 A CN201810069146 A CN 201810069146A CN 108376767 A CN108376767 A CN 108376767A
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Abstract
The present invention relates to a kind of red phosphorus/nitrogen-doped graphene composite negative pole materials and its preparation method and application, are first (2~4) in mass ratio by nitrogen-doped graphene and red phosphorus：(8~6) it is uniformly mixed, obtains mixture；Under protective atmosphere, obtained mixture is subjected to ball milling, obtains red phosphorus/nitrogen-doped graphene composite negative pole material.The present invention mixes grapheme material as base material using the nitrogen with good electronic conductivity, by with red phosphorus ball milling, it is mixed in grapheme material so that insulation particles of red phosphorus can be good at being dispersed in electric conductivity nitrogen during ball milling, this compound specific surface area is very big, improve whole conductivity and increase with the contact area of electrolyte, alleviate phosphorous-based materials structure caused by volume expansion meeting during the deintercalation of potassium ion and cave in and dusting and increase potassium ion diffusion rate；As kalium ion battery negative material, there is higher reversible appearance, excellent high rate performance and cyclical stability.
Description
Technical field
The present invention relates to field of batteries, and in particular to a kind of red phosphorus/nitrogen-doped graphene composite negative pole material and its preparation
Methods and applications.
Background technology
21 century, most Tough questions are exactly the energy and environment.The environment of large area can be caused without the reproducible energy
Pollution, nowadays the haze weather in many areas just illustrates such case.So it is particularly necessary to develop novel regenerative resource.
In recent years, it is lithium ion battery to be applied in industrialized production at most, but with the deep development lithium resource of lithium ion battery
Deficient problem it is increasingly severe, elemental lithium only accounts for 0.007% in the earth's crust, is a kind of rare metal, this not only makes lithium ion
The cost of battery is high, and considers out of permanent range, limits the development and application of lithium ion battery.
Sodium element and potassium element are in the first main group in the periodic table of elements with elemental lithium, and electrochemical properties are similar, also can
Enough realize the process of reversible charge and discharge, and the reserves of sodium element and potassium element in the earth's crust are very abundant, account for about respectively
2.09% and 2.36%.But due to the hydrogen potential of sodium-ion battery (- 2.71V vs E °) and lithium ion battery (- 3.04V vs
E °) compared to making the energy density of sodium-ion battery relatively low, keep it hindered in practical applications.The hydrogen of kalium ion battery
Current potential (- 2.93V vs E °) and lithium ion battery are very close to and higher energy density and low cost are so that potassium ion electricity
Pond has good foreground in practical applications.
Red phosphorus has the advantages such as resourceful, cheap and theoretical specific capacity (2596mAh/g) is higher.However, red
Phosphorus volume change in cyclic process is larger and lower electronic conductivity (10-14S/cm actual specific capacity caused by) is relatively low,
Showing the chemical property of red phosphorus cathode, there is still a need for further increase.
Invention content
It is an object of the invention to overcome problems of the prior art, it is multiple to provide a kind of red phosphorus/nitrogen-doped graphene
Negative material and its preparation method and application is closed, red phosphorus is evenly dispersed in nitrogen-doped graphene material in the composite negative pole material
In particle, it is applied in kalium ion battery, the high rate performance and cyclical stability of battery can be improved.
In order to achieve the above object, the present invention adopts the following technical scheme that：
Include the following steps：
(1) it is (2~4) in mass ratio by nitrogen-doped graphene and red phosphorus：(8~6) it is uniformly mixed, obtains mixture；
(2) under protective atmosphere, the mixture that step (1) is obtained carries out ball milling, and it is multiple to obtain red phosphorus/nitrogen-doped graphene
Close negative material.
Further, the preparation process of nitrogen-doped graphene includes：GO solution is mixed with cyanamide solution, under stiring in
60~80 DEG C are heated 1~4 hour, are then fallen water evaporation, are obtained the GO- melamine powders of Dark grey, GO- melamine powders are put into
In tube furnace, it is passed through temperature reaction after nitrogen, nitrogen-doped graphene is made, the mass ratio of wherein GO and cyanamide is (1~2)：(1
~50).
Further, temperature reaction is to be warming up to 800~1000 DEG C of 0.5~5h of reaction.
Further, 2~40h of ball milling in step (2).
Further, the protective atmosphere in step (2) is argon gas.
The technical solution of negative material of the present invention is：Nitrogen-doped graphene including ball milling and red phosphorus, wherein nitrogen are mixed
The mass ratio of miscellaneous graphene and red phosphorus is (2~4)：(8~6).
Further, particle of the negative material by average grain diameter in 40~80nm forms.
Red phosphorus/nitrogen-doped graphene composite negative pole material as described above is preparing lithium ion battery, sodium-ion battery or potassium
Application in ion battery.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention mixes grapheme material as base material using the nitrogen with good electronic conductivity, and nitrogen mixes graphite
The mechanical performance and high-specific surface area that graphene in alkene has unique electronic transport property outstanding, by carrying out nitrogen ginseng to it
Live together reason can with modulation its electronic structure, improve its physical and chemical performance, and by with red phosphorus ball milling so that insulation red phosphorus
(P) particle can be good at being dispersed in during ball milling during electric conductivity nitrogen mixes grapheme material, this compound specific surface
Product is very big, improves the contact area of whole conductivity and increase and electrolyte, alleviates deintercalation of the phosphorous-based materials in potassium ion
The structure caused by volume expansion meeting caves in and dusting and increases potassium ion diffusion rate in the process.This material conduct
Kalium ion battery negative material, preparation method is simple, and with higher reversible appearance, excellent high rate performance and stable circulation
Property, it is a kind of lithium ion battery negative material having very much application potential.
When red phosphorus of the present invention/nitrogen-doped graphene composite negative pole material is as kalium ion battery negative material, electricity obtained
Pond is in the case where electric current is 1300mA/g test conditions, and coulombic efficiency 83.8%~84.2%, first week discharge capacity are for the first time
1596mAh/g~2450mAh/g, for capacity almost without decaying, cyclical stability is high after recycling 100 weeks；And with reference to sample red phosphorus/
Coulombic efficiency 77% is recycling carbon nano tube compound material although discharge capacity can reach 1700mAh/g for the first time for the first time
Just have apparent capacity attenuation within 20 weeks or so, by 100 weeks after capacity decline to 500mAh/g hereinafter, show red phosphorus in the present invention/
Nitrogen-doped graphene composite negative pole material can generate specific mating reaction.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram that the nitrogen prepared in embodiment 1 mixes graphene；
Fig. 2 is the XRD diagram of the red phosphorus/nitrogen-doped graphene composite material prepared in embodiment 1；
Fig. 3 is the scanning electron microscope diagram of the red phosphorus/nitrogen-doped graphene composite material prepared in embodiment 1；
Fig. 4 is red phosphorus/nanometer that the red phosphorus/nitrogen-doped graphene composite material prepared in embodiment 1 is prepared with comparative example 1
The cycle specific discharge capacity figure of pipe composite material.
Specific implementation mode
The present invention is described in further details below in conjunction with the accompanying drawings.
The preparation method of the present invention includes the following steps：
(1) GO (graphene oxide) solution is mixed with cyanamide solution, is heated 1~4 hour in 60~80 DEG C under stiring,
Then water evaporation is fallen, obtains the GO- melamine powders of Dark grey, GO- melamine powders are put into tube furnace, is risen after being passed through nitrogen
Nitrogen-doped graphene is made to 0.5~5h is heated at 800~1000 DEG C in temperature, and the mass ratio of wherein GO and cyanamide is (1~2)：(1
~50) nitrogen-doped graphene, is made.
(2) a certain amount of nitrogen-doped graphene and red phosphorus are put into ball grinder after mixing, are passed through argon gas protection gas,
Then 2~40h of ball milling is carried out, red phosphorus/nitrogen-doped graphene composite negative pole material is made.The quality of nitrogen-doped graphene and red phosphorus
Than for (2~4)：(8~6).
The present invention also provides a kind of kalium ion batteries, there is cathode, anode, electrolyte and diaphragm composition, wherein cathode material
Material is the above-mentioned red phosphorus/nitrogen-doped graphene composite material of the present invention.
The present invention is described in further details below by specific embodiment.
Embodiment 1：
GO solution is mixed with cyanamide solution, is heated 2 hours in 70 DEG C under stiring, then water evaporation is fallen, obtains depth
The GO- melamine powders of grey, GO- melamine powders are put into tube furnace, are passed through after nitrogen to be warming up at 900 DEG C and are heated 2h, make
Nitrogen-doped graphene is obtained, the wherein mass ratio of graphene oxide and cyanamide is 1：1；By nitrogen-doped graphene obtained and red phosphorus with
3:7 mass ratio is put into ball grinder after mixing, ball milling 40h, and red phosphorus/nitrogen-doped graphene composite negative pole material is made.
Fig. 1 is the scanning electron microscope diagram that nitrogen manufactured in the present embodiment mixes graphene, from figure 1 it appears that nitrogen
It is in gauze-like to mix graphene, and lamella is mutually folded and crimped at edge.
Fig. 2 is the XRD diagram of red phosphorus manufactured in the present embodiment/nitrogen-doped graphene composite material, as it is clear from fig. 2 that obtained
Red phosphorus/nitrogen-doped graphene composite material is indefinite kenel.
Fig. 3 is the scanning electron microscope diagram of red phosphorus manufactured in the present embodiment/nitrogen-doped graphene composite material, from Fig. 3
As can be seen that nitrogen-doped graphene is closely integrated into about 40 nano particle of average grain diameter with red phosphorus.
The graphene of the red phosphorus of preparation and N doping and conductive agent and adhesive are mixed and made into slurries, are then coated in copper
On foil, after vacuum drying and cutting, phosphorus carbon electrode is made, phosphorus carbon electrode assembles button with potassium piece in vacuum glove box
2016 batteries test the chemical property of the graphene composite material of red phosphorus/N doping in the voltage range of 0.01-2V,
Electric current is under 1300mA/g test conditions, and the results are shown in Figure 4, for the first time coulombic efficiency 84%, and discharge capacity is for the first time
2450mAh/g, and recycle 100 weeks after capacity almost without decaying.
Embodiment 2：
GO solution is mixed with cyanamide solution, is heated 1 hour in 60 DEG C under stiring, then water evaporation is fallen, obtains depth
The GO- melamine powders of grey, GO- melamine powders are put into tube furnace, are passed through after nitrogen to be warming up at 800 DEG C and are heated 5h, make
Nitrogen-doped graphene is obtained, the wherein mass ratio of graphene oxide and cyanamide is 1：50；By nitrogen-doped graphene obtained and red phosphorus
With 4:6 mass ratio is put into ball grinder after mixing, ball milling 20h, and red phosphorus/N doping of about 60 nanometers of average grain diameter is made
Graphene composite negative pole.
The graphene of the red phosphorus of preparation and N doping and conductive agent and adhesive are mixed and made into slurries, are then coated in copper
On foil, after vacuum drying and cutting, phosphorus carbon electrode is made, phosphorus carbon electrode assembles button with potassium piece in vacuum glove box
2016 batteries test the chemical property of the graphene composite material of red phosphorus/N doping in the voltage range of 0.01-2V,
Electric current is under 1300mA/g test conditions, and coulombic efficiency 83.8% and first all discharge capacities are 1596mAh/g for the first time.
Embodiment 3：
GO solution is mixed with cyanamide solution, is heated 4 hours in 80 DEG C under stiring, then water evaporation is fallen, obtains depth
The GO- melamine powders of grey, GO- melamine powders are put into tube furnace, are passed through after nitrogen to be warming up at 1000 DEG C and are heated 0.5h,
Nitrogen-doped graphene is made, the wherein mass ratio of graphene oxide and cyanamide is 2：1, nitrogen-doped graphene is made, obtained nitrogen is mixed
Miscellaneous graphene；By nitrogen-doped graphene obtained and red phosphorus with 2:8 mass ratio is put into ball grinder after mixing, ball milling
Red phosphorus/nitrogen-doped graphene composite negative pole material of about 80 nanometers of average grain diameter is made in 2h.
The graphene of the red phosphorus of preparation and N doping and conductive agent and adhesive are mixed and made into slurries, are then coated in copper
On foil, after vacuum drying and cutting, phosphorus carbon electrode is made, phosphorus carbon electrode assembles button with potassium piece in vacuum glove box
2016 batteries test the chemical property of the graphene composite material of red phosphorus/N doping in the voltage range of 0.01-2V,
Electric current is under 1300mA/g test conditions, and coulombic efficiency 84.2% and first all discharge capacities are 1665mAh/g for the first time.
Comparative example 1：
According to above example it is found that the mass ratio of nitrogen-doped graphene and red phosphorus is 3:7 and ball milling 40h is made red
Phosphorus/nitrogen-doped graphene composite negative pole material chemical property is preferable.Therefore with this condition, prepared with same preparation condition
Red phosphorus/carbon nanotube composite negative pole material, the i.e. mass ratio of carbon nanotube and red phosphorus are 3:7 are put into ball grinder, are passed through argon gas
Protect gas, ball milling 40h.
Fig. 4 is red phosphorus/nanometer that the red phosphorus/nitrogen-doped graphene composite material prepared in embodiment 1 is prepared with comparative example 1
The cycle specific discharge capacity figure of pipe composite material.The result shows that red phosphorus/carbon nano tube compound material for the first time coulombic efficiency 77% with
And discharge capacity is 1700mAh/g for the first time, and just has apparent capacity attenuation at 20 weeks or so, by 100 weeks after capacity decline
To 500mAh/g hereinafter, and the graphene composite material of red phosphorus/N doping has higher coulombic efficiency for the first time 84% and head
Secondary discharge capacity be 2450mAh/g, and recycle 100 weeks after capacity almost without decaying, illustrate this material have compared with Gao Xun
Ring stability is a kind of kalium ion battery negative material having very much application potential.
Red phosphorus/nitrogen-doped graphene composite material of the present invention, is that red phosphorus and nitrogen-doped graphene (NG) ball milling obtain
The P-NG compounds of unbodied Nanoparticulate, are characterized by electro-chemical test, material of the present invention all have good potassium from
Sub- deintercalation ability, and abundant raw material, it is of low cost, it prepares simply, being expected to very much, which becomes a kind of kalium ion battery of useization, bears
Pole material.
The present invention will be passed through nitrogen in graphite oxide tube furnace, nitrogen-doped graphene (NG) be made after high-temperature heating, then
With red phosphorus mixing and ball milling, the P-NG kalium ion battery negative materials of unbodied Nanoparticulate are obtained, the present invention provides one
Red phosphorus/nitrogen-doped graphene composite material of the kind with highly electron conductive and alleviation volume expansion is negative as kalium ion battery
Pole material, wherein nitrogen-doped graphene have high conductivity material, by ball milling so that red phosphorus is uniformly dispersed in N doping stone
In black alkene material granule, the conductivity and discharge cycles stability of phosphorus are effectively improved, experiment shows this kind of material and with higher
Reversible capacity, excellent high rate performance and cyclical stability.
Claims (8)
1. a kind of preparation method of red phosphorus/nitrogen-doped graphene composite negative pole material, it is characterised in that：Include the following steps：
(1) it is (2~4) in mass ratio by nitrogen-doped graphene and red phosphorus：(8~6) it is uniformly mixed, obtains mixture；
(2) under protective atmosphere, the mixture that step (1) is obtained carries out ball milling, obtains red phosphorus/nitrogen-doped graphene Compound Negative
Pole material.
2. a kind of preparation method of red phosphorus/nitrogen-doped graphene composite negative pole material according to claim 1, feature exist
In：The preparation process of nitrogen-doped graphene includes：GO solution is mixed with cyanamide solution, heats 1 in 60~80 DEG C under stiring
~4 hours, then water evaporation is fallen, obtains the GO- melamine powders of Dark grey, GO- melamine powders are put into tube furnace, are passed through
The mass ratio of temperature reaction after nitrogen, obtained nitrogen-doped graphene, wherein GO and cyanamide is (1~2)：(1~50).
3. a kind of preparation method of red phosphorus/nitrogen-doped graphene composite negative pole material according to claim 2, feature exist
In：Temperature reaction is to be warming up to 800~1000 DEG C of 0.5~5h of reaction.
4. a kind of preparation method of red phosphorus/nitrogen-doped graphene composite negative pole material according to claim 1, feature exist
In：2~40h of ball milling in step (2).
5. a kind of preparation method of red phosphorus/nitrogen-doped graphene composite negative pole material according to claim 1, feature exist
In：Protective atmosphere in step (2) is argon gas.
6. a kind of red phosphorus/nitrogen-doped graphene composite negative pole material, it is characterised in that：Nitrogen-doped graphene including ball milling
And red phosphorus, the wherein mass ratio of nitrogen-doped graphene and red phosphorus is (2~4)：(8~6).
7. a kind of red phosphorus/nitrogen-doped graphene composite negative pole material according to claim 6, it is characterised in that：The cathode
Particle of the material by average grain diameter in 40~80nm forms.
8. red phosphorus as claimed in claim 6/nitrogen-doped graphene composite negative pole material is preparing lithium ion battery, sodium-ion battery
Or the application in kalium ion battery.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301178A (en) * | 2018-08-17 | 2019-02-01 | 福建新峰二维材料科技有限公司 | A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus |
| CN109390572A (en) * | 2018-10-12 | 2019-02-26 | 大连海事大学 | A kind of phosphorus sulphur/carbon composite and its preparation and application |
| CN110190256A (en) * | 2019-05-23 | 2019-08-30 | 广东工业大学 | A kind of antimony oxide/nitrogen-doped graphene composite material and preparation method and application |
| CN110492105A (en) * | 2019-08-26 | 2019-11-22 | 东莞维科电池有限公司 | The anode pole piece of a kind of positive electrode and its preparation and obtained lithium ion battery |
| CN111029549A (en) * | 2019-12-16 | 2020-04-17 | 成都爱敏特新能源技术有限公司 | High-performance lithium ion battery cathode structure and preparation method thereof |
| CN111082028A (en) * | 2019-12-31 | 2020-04-28 | 中南大学 | High-capacity negative electrode material, preparation method and lithium ion battery |
| CN112420999A (en) * | 2020-10-13 | 2021-02-26 | 天津大学 | Phosphorus-based negative electrode material with coating structure and preparation method and application thereof |
| CN113023713A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Preparation method of red phosphorus/graphene composite roll |
| CN113023697A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Red phosphorus/graphene composite roll |
| CN113307247A (en) * | 2021-06-17 | 2021-08-27 | 西安交通大学 | Preparation method of porous hard carbon/red phosphorus composite material |
| CN113437281A (en) * | 2021-05-31 | 2021-09-24 | 天津市天大赛达协同创新科技研究院有限公司 | Black phosphorus-based negative electrode material and preparation method thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109301178A (en) * | 2018-08-17 | 2019-02-01 | 福建新峰二维材料科技有限公司 | A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus |
| CN109390572A (en) * | 2018-10-12 | 2019-02-26 | 大连海事大学 | A kind of phosphorus sulphur/carbon composite and its preparation and application |
| CN110190256A (en) * | 2019-05-23 | 2019-08-30 | 广东工业大学 | A kind of antimony oxide/nitrogen-doped graphene composite material and preparation method and application |
| CN110492105A (en) * | 2019-08-26 | 2019-11-22 | 东莞维科电池有限公司 | The anode pole piece of a kind of positive electrode and its preparation and obtained lithium ion battery |
| CN110492105B (en) * | 2019-08-26 | 2022-11-25 | 东莞维科电池有限公司 | Positive electrode material, positive electrode plate prepared from positive electrode material and lithium ion battery obtained from positive electrode plate |
| CN111029549A (en) * | 2019-12-16 | 2020-04-17 | 成都爱敏特新能源技术有限公司 | High-performance lithium ion battery cathode structure and preparation method thereof |
| CN111082028A (en) * | 2019-12-31 | 2020-04-28 | 中南大学 | High-capacity negative electrode material, preparation method and lithium ion battery |
| CN112420999A (en) * | 2020-10-13 | 2021-02-26 | 天津大学 | Phosphorus-based negative electrode material with coating structure and preparation method and application thereof |
| CN113023697A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Red phosphorus/graphene composite roll |
| CN113023713A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Preparation method of red phosphorus/graphene composite roll |
| CN113437281A (en) * | 2021-05-31 | 2021-09-24 | 天津市天大赛达协同创新科技研究院有限公司 | Black phosphorus-based negative electrode material and preparation method thereof |
| CN113307247A (en) * | 2021-06-17 | 2021-08-27 | 西安交通大学 | Preparation method of porous hard carbon/red phosphorus composite material |
| CN114420936A (en) * | 2022-03-29 | 2022-04-29 | 太原科技大学 | Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof |
| CN114420936B (en) * | 2022-03-29 | 2022-05-27 | 太原科技大学 | Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof |
| CN114975925A (en) * | 2022-05-24 | 2022-08-30 | 广东凯金新能源科技股份有限公司 | Phosphorus-graphene doped composite graphite negative electrode material and preparation method thereof |
| CN114975925B (en) * | 2022-05-24 | 2024-06-07 | 广东凯金新能源科技股份有限公司 | Phosphorus-graphene doped composite graphite negative electrode material and preparation method thereof |
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