CN107749458A - A kind of nitrogen phosphorus doping graphene composite material and preparation method thereof, lithium ion battery negative electrode - Google Patents
A kind of nitrogen phosphorus doping graphene composite material and preparation method thereof, lithium ion battery negative electrode 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
- H01M4/362—Composites
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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
- 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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of nitrogen phosphorus doping graphene composite material and preparation method thereof, lithium ion battery negative electrode, belong to lithium ion battery material preparing technical field.The preparation method of the present invention, comprises the following steps：1) magnesia is added in nitrogen phosphorus inorganic compound solution and be uniformly dispersed, filtered, dry, obtain magnesia/nitrogen phosphorus compound；It is transferred to after magnesia/nitrogen phosphorus compound and nanocatalyst are mixed in reactor as matrix, is passed through hydrocarbon gas while 800~900 DEG C of 1~3h of insulation, insulation, obtains Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material；2) magnesia and nanocatalyst in Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material are removed using non-oxidizing acid, then filters, dries, produce.The preparation method of the present invention, it is possible to increase electric conductivity, specific capacity and the tap density of nitrogen phosphorus doping graphene composite material, while the cooperative effect between nitrogen and phosphorus is relied on, improve the specific capacity of its grapheme material.
Description
Technical field
The present invention relates to a kind of nitrogen phosphorus doping graphene composite material and preparation method thereof, lithium ion battery negative electrode,
Belong to lithium ion battery material preparing technical field.
Background technology
Lithium ion battery with its energy density is high, cycle life is high, advantages of environment protection and be widely used in electronic vapour
The fields such as car, number, electric tool and its energy storage.And negative material be form lithium ion battery key component, existing market
The negative material of change is based on native graphite, Delanium but it has the problem of gram volume is relatively low, although silicon-carbon class gram is held
Amount is high, but expansion rate is high and efficiency is low first causes it to be difficult to industrialization, while above-mentioned material has electric conductivity and security
Can be poor the problems such as.It is big with its conductance height, mechanical strength and graphene is a kind of novel anode material to grow up in recent years
The advantages that and applied to the field such as lithium ion battery negative material, conductive agent, but it has that efficiency is low, tap density is small first
The defects of, limit its application in terms of lithium ion battery.Although graphene can be improved by graphene nitrating and hydro-thermal method
The specific capacity and its tap density of material, but DeGrain and process are complicated, for example application publication number is
CN105565306A Chinese invention patent discloses a kind of high density nitrogen-doped graphene and preparation method thereof, and this method is main
By the specific capacity of the doping nitrogen source raising material in graphene oxide solution, and pass through the vibration density that hydro-thermal method improves material
Degree, but its tap density increase rate unobvious, material is easily reunited and the poor repeatability of method, have impact on lithium ion battery
The raising of energy density.
The content of the invention
It is an object of the invention to provide a kind of preparation method of nitrogen phosphorus doping graphene composite material, the nitrogen phosphorus being prepared
Doped graphene composite has the advantages of tap density is big, specific capacity is high.
Present invention also offers a kind of nitrogen phosphorus doping graphene composite material and lithium ion battery negative electrode.
In order to realize the above object technology used by the preparation method of the nitrogen phosphorus doping graphene composite material of the present invention
Scheme is：
A kind of preparation method of nitrogen phosphorus doping graphene composite material, comprises the following steps：
1) magnesia is added in nitrogen phosphorus inorganic compound solution and be uniformly dispersed, filtered, dry, obtain magnesia/nitrogen phosphorus
Compound；It is transferred to after magnesia/nitrogen phosphorus compound is well mixed with nanocatalyst in reactor as matrix, 800
~900 DEG C of 1~3h of insulation, are passed through hydrocarbon gas while insulation, obtain Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material；It is described
Nanocatalyst be Nanoscale Iron, nanometer cobalt, one kind in nano nickel；
2) magnesia and nano-catalytic in Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material are removed using non-oxidizing acid
Agent, then filter, dry, produce.
Template synthesis nano material have flexibility is strong, prevent from reuniting and the pattern of accurate control material and structure it is excellent
Put and paid attention to by researcher, the preparation method of nitrogen phosphorus doping graphene composite material of the invention, using magnesia as template
Agent, synthetic nitrogen phosphorus doping graphene composite material, have the advantages that process is simple, control is accurate and doping is homogeneous；Chemical gaseous phase
The advantages of deposition has depositing homogeneous, uniformity high and its can also deposited between the space of material, gained sedimentary consistency
Height, the tap density of negative material can be significantly improved.
The preparation method of the nitrogen phosphorus doping graphene composite material of the present invention, it is inorganization that nitrogen phosphorus is adulterated in graphene oxide
Compound, the electric conductivity of nitrogen phosphorus doping graphene composite material is improved, while by the cooperative effect between nitrogen and phosphorus, improve its stone
The specific capacity of black alkene material；In addition, using the preparation method of the present invention, the ratio table of obtained nitrogen phosphorus doping graphene composite material
Area is big, pore volume is high, it is possible to increase the imbibition liquid-keeping property of material；Mechanical strength is high simultaneously, structure is more stable, except can enter
One step is improved outside the specific capacity of nitrogen phosphorus doping graphene, moreover it is possible to the expansion of padded coaming charge and discharge process, improves the circulation of material
Performance.
The particle diameter of the nanocatalyst is 10~500nm.The mass ratio of the nanocatalyst and magnesia be 1~
10:10。
The hydrocarbon gas is methane or acetylene.Hydrocarbon gas is passed through while insulation can deposit to obtain graphene.
The nitrogen phosphorus inorganic compound is any one or a few in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate.Using
The nitrogen phosphorus inorganic compound can reduce the preparation cost of nitrogen phosphorus doping graphene composite material.
The mass percent concentration of nitrogen phosphorus inorganic compound is 0.9~12% in the nitrogen phosphorus inorganic compound solution.
Preferably, in step 1), the mass ratio of nitrogen phosphorus inorganic compound is in magnesia and nitrogen phosphorus inorganic compound solution
0.1~1:1~10.In the Surface coating nitrogen phosphorus inorganic compound of a small amount of nano magnesia, it can leave and receive after removing template is removed
Metre hole hole.Nitrogen P elements adsorb the activity reduction for the electron transfer rate reduction material on nano aperture surface, improving its material
The activity of material surface improves the efficiency first and its structural stability of material.
Preferably, the particle diameter of the magnesia is 50~500nm.
The preparation method of the magnesia comprises the following steps：Soluble magnesium saline solution and soluble carbonate salt is water-soluble
After liquid mixing, 1~6h is reacted under conditions of pressure is 1~5MPa, temperature is 100~200 DEG C, then filters, dry, forge
Burn, produce., can also after filtration, to generation in order to remove the impurity of the mgo surface of generation when preparing magnesia
Magnesia washed.The magnesium carbonate that calcining makes magnesium salts be generated with carbonate reaction is thermally decomposed to generate magnesia.After calcining
When the magnesia particle diameter of generation is larger, pulverization process can also be further carried out, obtains the smaller magnesia of particle diameter.The calcining
Temperature be 400~600 DEG C.
The soluble magnesium salt is one kind in magnesium chloride, magnesium sulfate, magnesium nitrate.Soluble magnesium in soluble magnesium salting liquid
The mass percent concentration of salt is 1~20%.
The soluble carbonate salt is one kind in sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus.Soluble carbonic acid
The mass percent concentration of soluble carbonate salt is 1~20% in salting liquid.
The soluble magnesium salt and the mol ratio of soluble carbonate salt are 1:1~1.1.
The mass fraction of magnesia is 0.1~2% in the Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material.Magnesia contains
When measuring excessive, removing a large amount of nano apertures left after magnesia influences its tap density, and appropriate magnesia both can be for it
The graphene that is vapor-deposited afterwards provides passage, the vibration density for the nitrogen phosphorus doping graphene composite material that also influence will not be prepared
Degree produces considerable influence.
Magnesia and nanocatalyst in Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material is removed using non-oxidizing acid
When, the method for acidleach can be used to remove.It can also be stirred during acidleach.The non-oxidizing acid is in hydrochloric acid, HBr, HF
One kind.The concentration of the hydrochloric acid is 1~10%.In step 2), in order to remove the non-oxidizable of filtered material remained on surface
The impurity such as acid, the material after removal magnesia can also be washed.
Technical scheme is used by the nitrogen phosphorus doping graphene composite material of the present invention：
Nitrogen phosphorus doping graphene composite material made from a kind of preparation method of above-mentioned nitrogen phosphorus doping graphene composite material.
The nitrogen phosphorus doping graphene of the present invention is made using the above method, has higher tap density, pore volume and Bi Biao
Area, during as lithium ion battery negative material, there is higher specific capacity, and the head of lithium ion battery can be significantly improved
Secondary efficiency and cycle performance, reduce the resistivity of lithium ion battery.
Technical scheme is used by the lithium ion battery negative electrode of the present invention：
A kind of lithium ion battery negative electrode using above-mentioned nitrogen phosphorus doping graphene composite material.
The lithium ion battery negative electrode of the present invention, the efficiency first and cyclicity of lithium ion battery can be significantly improved
Energy, reduce the resistivity of lithium ion battery.
Brief description of the drawings
Fig. 1 is SEM figure of the nitrogen phosphorus doping graphene composite material of the preparation of embodiment 1 under low multiplication factor；
Fig. 2 is SEM figure of the nitrogen phosphorus doping graphene composite material of the preparation of embodiment 1 under high-amplification-factor.
Embodiment
Technical scheme is further described below in conjunction with embodiment.
Embodiment 1
The preparation method of the nitrogen phosphorus doping graphene composite material of the present embodiment, comprises the following steps：
1) carbon for being 10% by magnesium chloride brine 95mL and mass percent concentration that mass percent concentration is 10%
Acid sodium aqueous solution 111mL is mixed, and is then transferred into autoclave, anti-under conditions of pressure is 3MPa, temperature is 180 DEG C
3h is answered, filters, wash, dry afterwards, be then transferred in tube furnace, 6h is calcined at 500 DEG C, crushes, it is 200nm's to obtain particle diameter
Magnesium oxide particle；
2) 10g ammonium phosphate is added in 90mL second distillation aqueous solvent, ultrasonic disperse is uniform, then adds 1g steps
1) magnesium oxide particle made from, stirs, and filters, is dried to obtain magnesia/nitrogen phosphorus compound, afterwards with 0.5g Nanoscale Irons
It is transferred to after (particle diameter 100nm) catalyst is well mixed in tube furnace, is warming up to 850 DEG C of insulation 2h deposited graphite alkene, insulation
While be passed through methane gas, Temperature fall to room temperature, obtains Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material afterwards；Magnesia
The mass percent for accounting for Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material is 0.5%；
3) it is obtained nitrogen phosphorus graphene in 11g steps 2)/magnesium oxide composite material is added to 100mL mass percents is dense
Spend in the hydrochloric acid for 5%, stir 1h, filtering, second distillation water washing, dry, produce.
The nitrogen phosphorus doping graphene composite material of the present embodiment is made using above-mentioned preparation method, and its SEM figure is shown in Fig. 1 and figure
2, as seen from Figure 2, the surface of the nitrogen phosphorus doping graphene composite material of the present embodiment has hole.
The lithium ion battery negative electrode of the present embodiment, using the nitrogen phosphorus doping graphene composite material of the present embodiment as negative
Pole active material, it is prepared using the preparation method comprised the following steps：By negative electrode active material and SP conductive agents and LA132
Binding agent and redistilled water are 93 according to mass ratio：3：4：150 ratio is mixed, and is uniformly dispersed to obtain cathode size,
Then cathode size is coated in copper foil surface, dried, roll-in, lithium ion battery negative electrode is made.
Embodiment 2
The preparation method of the nitrogen phosphorus doping graphene composite material of the present embodiment, comprises the following steps：
1) carbon for being 1% by magnesium sulfate solution 1200mL and mass percent concentration that mass percent concentration is 1%
Sour hydrogen sodium water solution 840mL mixing, is then transferred into autoclave, under conditions of pressure is 1MPa, temperature is 100 DEG C
6h is reacted, filters, wash, dry afterwards, be then transferred in tube furnace, 6h is calcined at 400 DEG C, crushes, it is 500nm to obtain particle diameter
Magnesium oxide particle；
2) 10g ammonium hydrogen phosphates are added in 1000mL second distillation aqueous solvents, ultrasonic disperse is uniform, then adds 1g steps
It is rapid 1) made from magnesium oxide particle, stir, filter, be dried to obtain magnesia/nitrogen phosphorus compound, afterwards with 0.1g nano nickels
It is transferred to after (particle diameter 50nm) catalyst is well mixed in tube furnace, is warming up to 800 DEG C of insulation 3h deposited graphite alkene, insulation
Methane gas is passed through simultaneously, Temperature fall to room temperature, obtains Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material afterwards；Magnesia accounts for
The mass percent of Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material is 1%；
3) it is Nitrogen-and Phosphorus-containing graphene made from 5g steps 2)/magnesium oxide composite material is added to 1000mL mass percents is dense
Spend in the hydrochloric acid for 1%, stir 1h, filtering, second distillation water washing, dry, produce.
The nitrogen phosphorus doping graphene composite material of the present embodiment is made using above-mentioned preparation method.
The lithium ion battery negative electrode of the present embodiment, the preparation method used, which is removed, is used as negative electrode active material for this implementation
Outside the nitrogen phosphorus doping graphene of example, remaining is completely the same as embodiment 1.
Embodiment 3
The preparation method of the nitrogen phosphorus doping graphene composite material of the present embodiment, comprises the following steps：
1) carbon for being 20% by magnesium nitrate aqueous solution 74mL and mass percent concentration that mass percent concentration is 20%
Acid sodium aqueous solution 75.9mL is mixed, and is then transferred into autoclave, under conditions of pressure is 5MPa, temperature is 200 DEG C
1h is reacted, filters, wash, dry afterwards, be then transferred in tube furnace, 6h is calcined at 600 DEG C, crushes, it is 50nm to obtain particle diameter
Magnesium oxide particle；
2) 10g ammonium dihydrogen phosphates are added in 1000mL second distillation aqueous solvents, after ultrasonic disperse is uniform, then add 1g
Magnesium oxide particle made from step 1), stirs, and filters, is dried to obtain magnesia/nitrogen phosphorus compound, afterwards with 1g nanometer cobalts
It is transferred to after (particle diameter 500nm) catalyst is well mixed in tube furnace, is warming up to 900 DEG C of insulation 1h deposited graphite alkene, insulation
While be passed through acetylene gas, Temperature fall to room temperature, obtains Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material afterwards；Magnesia
The mass percent for accounting for Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material is 2%；
3) Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material made from 20g steps 2) is added to 1000mL mass percents
Concentration is in 10% hydrochloric acid, stirs 1h, filtering, second distillation water washing, dries, produce.
The nitrogen phosphorus doping graphene composite material of the present embodiment is made using above-mentioned preparation method.
The lithium ion battery negative electrode of the present embodiment, the preparation method used, which is removed, is used as negative electrode active material for this implementation
Outside the nitrogen phosphorus doping graphene of example, remaining is completely the same as embodiment 1.
Embodiment 4
The preparation method of the nitrogen phosphorus doping graphene composite material of the present embodiment, comprises the following steps：
1) carbon for being 10% by magnesium chloride brine 95mL and mass percent concentration that mass percent concentration is 10%
Acid sodium aqueous solution 111mL is mixed, and is then transferred into autoclave, anti-under conditions of pressure is 3MPa, temperature is 150 DEG C
5h is answered, filters, wash, dry afterwards, be then transferred in tube furnace, in 500 DEG C of calciningsH, crush, it is 350nm's to obtain particle diameter
Magnesium oxide particle；
2) 10g ammonium dihydrogen phosphates are added in 500mL second distillation aqueous solvents, after ultrasonic disperse is uniform, then add 1g
Magnesium oxide particle made from step 1), stirs, and filters, is dried to obtain magnesia/nitrogen phosphorus compound, afterwards with 0.8g nanometers
It is transferred to after cobalt (particle diameter 10nm) catalyst is well mixed in tube furnace, is warming up to 850 DEG C of insulation 2h deposited graphite alkene, insulation
While be passed through acetylene gas, Temperature fall to room temperature, obtains Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material afterwards；Magnesia
The mass percent for accounting for Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material is 0.1%；
3) Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material made from 20g steps 2) is added to 1000mL mass percents
Concentration is in 10% hydrochloric acid, stirs 1h, filtering, second distillation water washing, dries, produce.
The nitrogen phosphorus doping graphene composite material of the present embodiment is made using above-mentioned preparation method.
The lithium ion battery negative electrode of the present embodiment, the preparation method used, which is removed, is used as negative electrode active material for this implementation
Outside the nitrogen phosphorus doping graphene of example, remaining is completely the same as embodiment 1.
Comparative example
The preparation method of the nitrogen phosphorus doping graphene composite material of comparative example, comprises the following steps：
10g ammonium dihydrogen phosphates are added in the graphene oxide dispersion that 1000mL mass percent concentrations are 1%, stirred
Mix uniformly, be transferred in tube furnace and be passed through acetylene gas and sinter 3h in temperature for 800 DEG C, crush, produce afterwards.
The lithium ion battery negative electrode of comparative example, the preparation method used, which is removed, is used as negative electrode active material for this comparative example
Nitrogen phosphorus doping graphene outside, remaining is completely the same as embodiment 1.
Experimental example
1) respectively according to national standard GB/T/24533-2009《Silicon/carbon/graphite in lithium ion batteries class negative material》Testing example 1
~4 and comparative example nitrogen phosphorus doping graphene composite material tap density, first specific capacity, efficiency, resistivity, specific surface area
And pore volume, test result are shown in Table 1.
The simulated battery used in test process is button cell, with the nitrogen phosphorus doping graphite of embodiment 1~4 and comparative example
Alkene composite is negative material, lithium piece is positive pole, with LiPF6/ EC+DEC is electrolyte (LiPF in electrolyte6Concentration be
1.2mol/L, EC and DEC volume ratio is 1 in the solvent used:1), with polythene PE, polypropylene PP and poly- second propylene PEP
Composite membrane is barrier film.Being assemblied in the glove box for be flushed with hydrogen gas for button cell is carried out, and chemical property is in the blue electric CT2001A in Wuhan
Carried out on type cell tester.Charging/discharging voltage scope control is in 0.005~2.0V, charge-discharge magnification 0.1C.
The physical and chemical performance of the nitrogen phosphorus doping graphene composite material of the embodiment 1~4 of table 1 and comparative example
As can be seen from Table 1, the nitrogen phosphorus doping graphene composite material of embodiment 1~4 in tap density and its compares surface
Product aspect is better than comparative example, the reason for this is that its specific surface area is increased using magnesium oxide template, while doped with nitrogen phosphorus in graphene
Material improves the electronic conductivity of material, so as to reduce the resistivity of its material and its improve the specific capacity hair of grapheme material
Wave, so as to improve its efficiency first.
2) the cycle performance test of soft bag lithium ionic cell
Negative plate is prepared as negative material using the nitrogen phosphorus doping graphene composite material of embodiment 1~4 and comparative example respectively,
Using LiFePO4 as positive electrode, with EC/DEC/PC (EC:DEC:PC=1:1:1) solvent is used as, with LiPF6For solute, with
The films of Celgard 2400 are barrier film, prepare 5Ah soft-package batteries C1, C2, C3, C4 and D1 respectively.
The efficiency first of soft bag lithium ionic cell made from test, cycle performance (0.1C/0.1C) respectively, method of testing ginseng
According to standard GB/T/T 24533-2009《Silicon/carbon/graphite in lithium ion batteries class negative material》；Put respectively according to lithium ion battery simultaneously
Capacitance and quality, calculate the mass energy density of soft bag lithium ionic cell.Test result is shown in Table 3.
The soft bag lithium ionic cell cycle performance of table 2
As shown in Table 2, using embodiment 1~4 nitrogen phosphorus doping graphene composite material soft-package battery cycle performance
Comparative example is significantly better than that, analysis reason is：It is compound that the big nitrogen phosphorus graphene of specific surface area can be prepared using template
Material, has that specific surface area is big, improves the imbibition ability of material, so as to improve the cycle performance of material；Meanwhile porous graphene
Big, the expansion in padded coaming charge and discharge process with mechanical strength height, specific surface area, improve the cycle performance of material.
3) imbibition, water retainability test
The imbibition to embodiment 1~4 and the nitrogen phosphorus doping graphene composite material of comparative example, liquid-keeping property are surveyed respectively
Examination.
Pole piece for test, imbibition ability are acted on the lithium ion battery negative electrode of embodiment 1~4 and comparative example
Method of testing be：Using 1mL buret, and Electolyte-absorptive VmL, it is added dropwise is dripped in pole piece one afterwards, and is counted
When, finish, record the time (t), it is V/t to obtain rate of liquid aspiration until the electrolyte of pole piece absorbs；Protect liquid rate method of testing：
Theoretical reservoir quantity m is calculated according to pole piece parameter1, and pole piece is placed into theoretical electrolyte, 24h is placed, weighs pole piece
The electrolyte m of absorption2, finally obtain and protect liquid rate=m2/m1* 100%.What imbibition, water retainability were tested the results are shown in Table 3.
The imbibition of the nitrogen phosphorus doping graphene composite material of the embodiment 1~4 of table 3 and comparative example, liquid-keeping property
| Project | Rate of liquid aspiration (mL/min) | Protect liquid rate (24h electrolyte contents/0h electrolyte contents) |
| Embodiment 1 | 3.8 | 95.1% |
| Embodiment 2 | 3.6 | 94.3% |
| Embodiment 3 | 3.5 | 94.2% |
| Embodiment 4 | 3.3 | 93.8% |
| Comparative example | 1.2 | 83.1% |
Known by table 3, using the imbibition liquid-keeping property of the negative plate of the nitrogen phosphorus doping graphene composite material of embodiment 1~4
Comparative example is significantly better than that, analysis reason is：The nitrogen phosphorus doping graphene composite wood prepared using chemical vapour deposition technique
Material has nano level hole, it is possible to increase the imbibition liquid-keeping property of negative plate.
Claims (10)
- A kind of 1. preparation method of nitrogen phosphorus doping graphene composite material, it is characterised in that：Comprise the following steps：1) magnesia is added in nitrogen phosphorus inorganic compound solution and be uniformly dispersed, filtered, dry, it is compound to obtain magnesia/nitrogen phosphorus Thing；It is transferred to after magnesia/nitrogen phosphorus compound is well mixed with nanocatalyst in reactor as matrix, 800~900 DEG C 1~3h of insulation, is passed through hydrocarbon gas while insulation, obtains Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material；Described nanometer Catalyst is one kind in Nanoscale Iron, nanometer cobalt, nano nickel；2) magnesia and nanocatalyst in Nitrogen-and Phosphorus-containing graphene/magnesium oxide composite material are removed using non-oxidizing acid, so Filter, dry afterwards, produce.
- 2. the preparation method of nitrogen phosphorus doping graphene composite material according to claim 1, it is characterised in that：The nitrogen phosphorus Inorganic compound is any one or a few in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate.
- 3. the preparation method of nitrogen phosphorus doping graphene composite material according to claim 1, it is characterised in that：The nitrogen phosphorus The mass percent concentration of nitrogen phosphorus inorganic compound is 0.9~12% in inorganic compound solution.
- 4. the preparation method of nitrogen phosphorus doping graphene composite material according to claim 1, it is characterised in that：The nanometer The mass ratio of catalyst and magnesia is 1~10:10.
- 5. the preparation method of nitrogen phosphorus doping graphene composite material according to claim 1, it is characterised in that：The oxidation The particle diameter of magnesium is 50~500nm.
- 6. the preparation method of the nitrogen phosphorus doping graphene composite material according to any one in Claims 1 to 5, its feature It is：The preparation method of the magnesia comprises the following steps：By soluble magnesium saline solution and the soluble carbonate salt aqueous solution After mixing, 1~6h is reacted under conditions of pressure is 1~5MPa, temperature is 100~200 DEG C, then filters, dry, calcining, Produce.
- 7. the preparation method of nitrogen phosphorus doping graphene composite material according to claim 6, it is characterised in that：The calcining Temperature be 400~600 DEG C.
- 8. the preparation method of nitrogen phosphorus doping graphene composite material according to claim 1, it is characterised in that：It is described nitrogenous The mass fraction of magnesia is 0.1~1% in phosphorus graphene/magnesium oxide composite material.
- A kind of 9. nitrogen phosphorus doping made from preparation method using nitrogen phosphorus doping graphene composite material as claimed in claim 1 Graphene composite material.
- A kind of 10. lithium ion battery negative electrode using nitrogen phosphorus doping graphene composite material as claimed in claim 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092710A (en) * | 2010-12-17 | 2011-06-15 | 中国科学院化学研究所 | Regular graphene and preparation method thereof |
| CN104045079A (en) * | 2014-06-25 | 2014-09-17 | 无锡格菲电子薄膜科技有限公司 | Method for epitaxially growing graphene on sapphire/epitaxial metal interface |
| CN104843691A (en) * | 2015-04-30 | 2015-08-19 | 深圳市德方纳米科技股份有限公司 | Graphene and preparation method thereof |
| CN106335897A (en) * | 2016-08-26 | 2017-01-18 | 中国人民大学 | Large single crystal double layer graphene and the preparation method thereof |
| CN107119263A (en) * | 2017-05-04 | 2017-09-01 | 天津理工大学 | A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode |
-
2017
- 2017-11-02 CN CN201711065416.1A patent/CN107749458A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092710A (en) * | 2010-12-17 | 2011-06-15 | 中国科学院化学研究所 | Regular graphene and preparation method thereof |
| CN104045079A (en) * | 2014-06-25 | 2014-09-17 | 无锡格菲电子薄膜科技有限公司 | Method for epitaxially growing graphene on sapphire/epitaxial metal interface |
| CN104843691A (en) * | 2015-04-30 | 2015-08-19 | 深圳市德方纳米科技股份有限公司 | Graphene and preparation method thereof |
| CN106335897A (en) * | 2016-08-26 | 2017-01-18 | 中国人民大学 | Large single crystal double layer graphene and the preparation method thereof |
| CN107119263A (en) * | 2017-05-04 | 2017-09-01 | 天津理工大学 | A kind of preparation method of vertical graphene/boron-doped diamond sensing electrode |
Non-Patent Citations (1)
| Title |
|---|
| XINLONG MA等: "phosphrous and Nitrogen Dual-doped Few-layered Porous Graphene: A high-performance Anode Material for Lithium-ion Batteries", 《APPLIED MATERIALS &INTERFACES》 * |
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