CN103035914A - Nickel sulfate sheet/graphene composite material as well as preparation method and application thereof - Google Patents
Nickel sulfate sheet/graphene composite material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nickel sulfate sheet/graphene composite material as well as a preparation method and application thereof. The nickel sulfate sheet/graphene composite material comprises nanoscale nickel sulfate and graphene, wherein NiS takes a sheet shape. Nickel sulfate sheets in the composite materials can be evenly arranged due to the dispersing and bearing effects of the graphene and have small sizes, so that the stability and the circulating stability of the nickel sulfate in the charge and discharge process can be effectively improved, and the composite material can be used as a lithium ion battery cathode material. The preparation method of the composite material is a one-step low-temperature preparation method, has the advantages of simple technique, low cost, short circle, low energy consumption and the like, and is suitable for large-scale industrial production. The nickel sulfate sheet/graphene composite material can be used as the lithium ion battery cathode material.
Description
Technical field
The present invention relates to the lithium ion battery field of compound material, be specifically related to a kind of nickel sulfide thin slice/graphene composite material and its preparation method and application.
Background technology
Lithium ion battery has the advantages such as operating voltage height, energy density is large, security performance is good, therefore in the portable type electronic products such as digital camera, mobile phone and notebook computer, be used widely, also have application prospect for electric bicycle and electric automobile.Present commercial lithium ion battery generally adopts the carbon back negative material, and such as graphite, although this material stability is higher, theoretical capacity only has 372mAhg
-1
Compare with material with carbon element, some transient metal sulfide has higher theoretical capacity, such as the theoretical capacity of NiS up to 589mAhg
-1This class transient metal sulfide has a general character: reversible reaction can occur with lithium metal in contained sulphur, and this reaction provides reversible capacity, and the transition metal discord lithium generation alloying of first embedding lithium formation/taking off alloying reaction, its process is:
M′
xS
y+2y?Li→x?M′+y?Li
2S
Although this reaction can provide higher capacity, because change in volume is larger in the removal lithium embedded process, cause the rapid decay of capacity.At present, effectively slow down capacity fast the method for decay generally be transient metal sulfide and other basis material to be carried out compound, comparatively ideal basis material is material with carbon element.In various material with carbon elements, Graphene is ideal basis material because of its high conductivity, high mechanical strength, large specific area and porosity.
Existing a lot of as the report that basis material prepares composite material with Graphene in the prior art, as disclosing a kind of transition metal oxide/graphene composite material among the Chinese patent application CN201110083375.5, be comprised of nanocrystalline transition metal oxide and Graphene, described transition metal oxide is MnO, Fe
2O
3, Cr
2O
3, Cu
2O, CuO or V
2O
5Transition metal oxide in this composite material is because the dispersion of Graphene and the carrying effect can evenly distribute and granularity is little, but stability and the cyclical stability of Effective Raise transition metal oxide in charge and discharge process.A kind of transition metal oxide/graphene nanometer composite electrode material used for lithium battery and preparation method thereof is disclosed among the Chinese patent application CN201010237027.4, it is the transition metal oxide of Graphene or graphene oxide modification, mode with physically encapsulation or chemical bonding between transition metal oxide and Graphene or the graphene oxide is connected, adopt a kind of in the following method: 1. will prepare the required precursor of transition metal oxide and Graphene (or graphene oxide) and be by weight and to 50: 100 in solvent evenly mix at 0.01: 100, in uniform temperature, reaction obtains nanometer combined electrode material under the pressure; 2. be to 50: 100 in solvent fully to mix at 0.01: 100 by weight with Graphene (or graphene oxide) and transition metal oxide, drying obtains nanometer combined electrode material; The preparation method is easy, easy to operate, is applicable to large-scale production, and the electrode material that makes has the conductivity of higher lithium ion and electronics, and the lithium battery specific capacity of assembling is high, good cycle, is suitable for electrode material of lithium battery.Chinese patent application CN201210254567.2 discloses a kind of transient metal sulfide/graphene composite material, is comprised of nano grade transition metal sulfide and Graphene, and described transient metal sulfide is Ni
2S
3, NiS, FeS, FeS
2, CoS, CoS
2, Cu
2S, CuS, MnS or MnS
2Transient metal sulfide in this composite material is because the dispersion of Graphene and the carrying effect can evenly distribute and granularity is little, but stability and the cyclical stability of Effective Raise transient metal sulfide in charge and discharge process can be used as lithium ion battery negative material.
Therefore, exploitation transient metal sulfide/graphene composite material has broad application prospects.
Summary of the invention
The invention provides the good nickel sulfide thin slice/graphene composite material of a kind of electrochemical stability and cyclical stability.
The present invention also provides a kind of preparation method of nickel sulfide thin slice/graphene composite material, and the method technique is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
The present invention finds that laminar nickel sulfide electrochemical stability and cyclical stability are better, if nickel sulfide thin slice and Graphene is compound, can be used to improve the chemical property, particularly cyclical stability of nickel sulfide thin slice.
A kind of nickel sulfide thin slice/graphene composite material is comprised of nanoscale nickel sulfide (NiS) and Graphene (G), and described nanoscale nickel sulfide is flaky texture.
In order further to improve the application performance of composite material, the weight percentage of Graphene is preferably 0.4%~20% in the described composite material, and more preferably 7.4%~15.2%.
The size of nickel sulfide thin slice is less, and easier covering is stated from the Graphene, and the electrochemical stability performance of composite material is better, so the present invention selects nanoscale nickel sulfide thin slice, and preferred, described nanoscale nickel sulfide thin slice is of a size of 100 nanometers~500 nanometers.Consider that from the angle that improves composite material combination property further preferred described nanoscale nickel sulfide thin slice is of a size of 200 nanometers~500 nanometers.
Preferably, nanoscale nickel sulfide thin slice is Uniform Dispersion in the described composite material.
The preparation method of described nickel sulfide thin slice/graphene composite material may further comprise the steps:
1) hydrate with nickeliferous salt or nickeliferous salt is dissolved in deionized water or the organic solvent, obtains with nickel ion Ni
2+Meter concentration is the solution of 0.01mol/L~0.1mol/L, adds graphene oxide (GO) again, through fully obtaining mixed solution after the dispersed with stirring;
The addition of described GO is 1%~50% of nickel sulfide theoretical weight, more preferably 20%~45%;
2) add sulfur-containing compound in the mixed solution with step 1), addition is 2~4 times of salt mole nickeliferous in the step 1), adds surfactant trisodium citrate (Na again
3C
6H
5O
72H
2O) or the hydrate of trisodium citrate, the addition of described surfactant is 1~3 times of salt mole nickeliferous in the step 1), be warming up to 160 ℃~240 ℃ after the sealing, react cooling after 12 hours~48 hours, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains nickel sulfide thin slice/graphene composite material.
Owing to generally be alkalescence after the dissolving of sulfur-containing compound raw material, under alkali condition, GO can be reduced into G through solvent thermal reaction, therefore needn't add in addition reducing agent.
In order to reach better invention effect, preferably:
Described nickeliferous salt can be selected the chloride of nickel, the fluoride of nickel, the nitrate of nickel, the sulfate of nickel, the oxalates of nickel or the acetate of nickel.
Described sulfur-containing compound can be selected vulcanized sodium, potassium sulfide, ammonium sulfide, sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate), thiopropionamide, thioacetamide, thiocarbamide or carbon disulfide.
Described organic solvent is ethanol, methyl alcohol, ethylene glycol, n-butyl alcohol, DMF, pyridine, ethylenediamine, benzene or toluene.
Step 2) in, further preferably in 170 ℃~220 ℃ reactions cooling after 12 hours~48 hours; Reaction temperature is high, and the time is long, and nickel sulfide easily forms, and graphene oxide easily is reduced into Graphene, but little on the impact of nickel sulfide lamina dimensions.
The temperature of described cooling does not have strict restriction, is operating as the master with suitable, generally can be cooled to 15 ℃~30 ℃ ambient temperature.
Described nickel sulfide thin slice/graphene composite material can be used as lithium ion battery negative material.
Compared with prior art, the present invention has following advantage:
1, the present invention adopts one-step method to prepare nickel sulfide thin slice/graphene composite material at low temperature, has that technique is simple, cost is low, the cycle is short, energy consumption is low and is fit to the advantage such as suitability for industrialized production.
2, owing to dispersion and the carrying effect of Graphene, the peptizaiton of mating surface activating agent can access the nickel sulfide thin slice that is evenly distributed in composite material, and the nickel sulfide lamina dimensions that obtains is little simultaneously, and lamina dimensions is 200~500 nanometers.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of embodiment 1 gained NiS thin slice/graphene composite material.
Fig. 2 is the transmission electron microscope photo of embodiment 1 gained NiS thin slice/graphene composite material.
Fig. 3 is the chemical property figure of embodiment 1 gained NiS thin slice/graphene composite material and pure NiS.
Embodiment
Embodiment 1
With NiCl
26H
2O is raw material, and it is dissolved in deionized water, is mixed with 80 milliliters with Ni
2+Meter concentration is the solution of 0.01mol/L, adds 32 milligrams of GO through fully making mixed solution after the dispersed with stirring again; (mole dosage of thiocarbamide is NiCl with thiocarbamide again
26H
23 times of O mole) be added to above-mentioned mixed solution, (mole dosage of trisodium citrate is NiCl to add trisodium citrate again
26H
21 times of O mole), the capacity that then is transferred to is in 100 milliliters the autoclave (compactedness 80%, percent by volume), then with the reactor sealing, 180 ℃ of lower reactions 24 hours, to naturally cool to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, 60 ℃ of lower vacuumizes obtain 0.085g NiS thin slice/graphene composite material with product, and wherein, the weight percentage of Graphene is 15.2%.
The X ray diffracting spectrum of the composite material of gained and transmission electron microscope photo are respectively such as Fig. 1 and Fig. 2, the composite material that can find out gained is NiS thin slice/graphene composite material, wherein NiS is laminar, and lamina dimensions is 200 nanometers~500 nanometers, and it is more even to distribute.
Comparative Examples 1
Adopt the method preparation among the Chinese patent application CN201210254567.2, specific as follows:
Except thiocarbamide is replaced with thioacetamide, and do not add outside the trisodium citrate, all the other operate with embodiment 1, make 0.10g NiS particle/graphene composite material, and wherein, the weight percentage of Graphene is 12.5%.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the composite material of gained the composite material of gained is NiS particle/graphene composite material, wherein NiS is graininess, and particle size is 50 nanometers~100 nanometers, and it is more even to distribute.
Comparative Examples 2
Except not adding the GO, all the other operate with embodiment 1, make the pure nanometer NiS particle of 0.06g.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the pure nanometer NiS particle of gained the product of gained is pure nanometer NiS particle, wherein NiS is graininess, and particle size is 100 nanometers~150 nanometers, and size is more even.
One, performance test
The pure nanometer NiS particle of the NiS particle for preparing with embodiment 1 gained NiS thin slice/G composite material, Comparative Examples 1 respectively/G composite material and Comparative Examples 2 preparations carries out electrochemical property test (constant current charge-discharge in the certain voltage scope) as lithium ion battery negative material, gained NiS thin slice/G composite material and pure nanometer NiS particle chemical property figure such as Fig. 3, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005~3V) test shows that cycle-index is at 1 o'clock, the capacity of NiS thin slice/G composite material is 800mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS thin slice/G composite material only is reduced to 536mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nanometer NiS particle is 578mAhg
-1, cycle-index is 35 o'clock, it only is 64mAhg that the capacity of pure nanometer NiS particle reduces rapidly
-1Cycle-index is 1 o'clock, and the capacity of NiS particle/G composite material is 726mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS particle/G composite material comparatively fast is reduced to 408mAhg
-1As seen compare with pure nanometer NiS particle, NiS particle/G composite material, the cyclical stability of NiS thin slice/G composite material obviously improves, and electrochemical stability is good.
Simultaneously, comparative example 1 and Comparative Examples 1, Comparative Examples 2 also can be found out, if do not use simultaneously graphene oxide and surfactant can't obtain laminar NiS.
Embodiment 2
With NiC
2O
42H
2O is raw material, and it is dissolved in the ethanol, is mixed with 80 milliliters with Ni
2+Meter concentration is the solution of 0.04mol/L, adds 87 milligrams of GO through fully making mixed solution after the dispersed with stirring again; Again with Na
2S(Na
2The mole dosage of S is NiC
2O
42H
22 times of O mole) be added to above-mentioned mixed solution, (the mole use amount of trisodium citrate is NiC to add trisodium citrate again
2O
42H
22 times of O mole), the capacity that then is transferred to is in 100 milliliters the autoclave (compactedness 80%, percent by volume), then with the reactor sealing, 220 ℃ of lower reactions 12 hours, to naturally cool to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, 60 ℃ of lower vacuumizes obtain 0.32g NiS thin slice/graphene composite material with product, and wherein, the weight percentage of Graphene is 10.7%.
Be NiS thin slice/graphene composite material from the X ray diffracting spectrum of the composite material of gained and the composite material that transmission electron microscope photo can be found out gained, wherein NiS is laminar, and lamina dimensions is 200 nanometers~500 nanometers, and it is more even to distribute.
Comparative Examples 3
Adopt the method preparation among the Chinese patent application CN201210254567.2, specific as follows:
Except not adding the trisodium citrate, all the other operate with embodiment 2, make 0.30g NiS particle/graphene composite material, and wherein, the weight percentage of Graphene is 10.5%.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the composite material of gained the composite material of gained is NiS particle/graphene composite material, wherein NiS is graininess, and particle size is 50 nanometers~100 nanometers, and it is more even to distribute.
Comparative Examples 4
Except not adding the GO, all the other operate with embodiment 2, make the pure nanometer NiS particle of 0.25g.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the pure nanometer NiS particle of gained the product of gained is pure nanometer NiS particle, wherein NiS is graininess, and particle size is 100 nanometers~150 nanometers, and size is more even.
Two, performance test
The pure nanometer NiS particle of the NiS particle for preparing with embodiment 2 gained NiS thin slice/G composite materials, Comparative Examples 3 respectively/G composite material and Comparative Examples 4 preparations carries out electrochemical property test as lithium ion battery negative material, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005~3V) test shows that cycle-index is at 1 o'clock, the capacity of NiS thin slice/G composite material is 782mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS thin slice/G composite material only is reduced to 557mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nanometer NiS particle is 562mAhg
-1, cycle-index is 35 o'clock, it only is 78mAhg that the capacity of pure nanometer NiS particle reduces rapidly
-1Cycle-index is 1 o'clock, and the capacity of NiS particle/G composite material is 701mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS particle/G composite material comparatively fast is reduced to 384mAhg
-1As seen compare with pure nanometer NiS particle, NiS particle/G composite material, the cyclical stability of NiS thin slice/G composite material obviously improves, and electrochemical stability is good.
Simultaneously, comparative example 2 and Comparative Examples 3, Comparative Examples 4 also can be found out, if do not use simultaneously graphene oxide and surfactant can't obtain laminar NiS.
Embodiment 3
With Ni (NO
3)
26H
2O is raw material, and it is dissolved in ethylene glycol, is mixed with 80 milliliters with Ni
2+Meter concentration is the solution of 0.06mol/L, adds 108 milligrams of GO through fully making mixed solution after the dispersed with stirring again; (the mole use amount of thioacetamide is Ni (NO with thioacetamide again
3)
26H
24 times of O mole) join above-mentioned mixed solution, (the mole use amount of trisodium citrate is Ni (NO to add trisodium citrate again
3)
26H
23 times of O mole), the capacity that then is transferred to is in 100 milliliters the autoclave (compactedness 80%, percent by volume), then with the reactor sealing, 170 ℃ of lower reactions 48 hours, to naturally cool to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, 60 ℃ of lower vacuumizes obtain 0.47g NiS thin slice/graphene composite material with product, and wherein, the weight percentage of Graphene is 9.1%.
Be NiS thin slice/graphene composite material from the X ray diffracting spectrum of the composite material of gained and the composite material that transmission electron microscope photo can be found out gained, wherein NiS is laminar, and lamina dimensions is 200 nanometers~500 nanometers, and it is more even to distribute.
Comparative Examples 5
Adopt the method preparation among the Chinese patent application CN201210254567.2, specific as follows:
Except not adding the trisodium citrate, all the other operate with embodiment 3, make 0.51g NiS particle/graphene composite material, and wherein, the weight percentage of Graphene is 9.6%.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the composite material of gained the composite material of gained is NiS particle/graphene composite material, wherein NiS is graininess, and particle size is 50 nanometers~100 nanometers, and it is more even to distribute.
Comparative Examples 6
Except not adding the GO, all the other operate with embodiment 3, make the pure nanometer NiS particle of 0.38g.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the pure nanometer NiS particle of gained the product of gained is pure nanometer NiS particle, wherein NiS is graininess, and particle size is 100 nanometers~150 nanometers, and size is more even.
Three, performance test
The pure nanometer NiS particle of the NiS particle for preparing with embodiment 3 gained NiS thin slice/G composite materials, Comparative Examples 5 respectively/G composite material and Comparative Examples 6 preparations carries out electrochemical property test as lithium ion battery negative material, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005~3V) test shows that cycle-index is at 1 o'clock, the capacity of NiS thin slice/G composite material is 810mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS thin slice/G composite material only is reduced to 577mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nanometer NiS particle is 601mAhg
-1, cycle-index is 35 o'clock, it only is 102mAhg that the capacity of pure nanometer NiS particle reduces rapidly
-1Cycle-index is 1 o'clock, and the capacity of NiS particle/G composite material is 739mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS particle/G composite material comparatively fast is reduced to 416mAhg
-1As seen compare with pure nanometer NiS particle, NiS particle/G composite material, the cyclical stability of NiS thin slice/G composite material obviously improves, and electrochemical stability is good.
Simultaneously, comparative example 3 and Comparative Examples 5, Comparative Examples 6 also can be found out, if do not use simultaneously graphene oxide and surfactant can't obtain laminar NiS.
Embodiment 4
With Ni (CH
3COO)
24H
2O is raw material, and it is dissolved in ethylenediamine, is mixed with 80 milliliters with Ni
2+Meter concentration is the solution of 0.1mol/L, adds 145 milligrams of GO through fully making mixed solution after the dispersed with stirring again; Again with Na
2S
2O
3(Na
2S
2O
3Mole dosage be Ni (CH
3COO)
24H
22.5 times of O mole) join above-mentioned mixed solution, (the mole use amount of trisodium citrate is Ni (CH to add trisodium citrate again
3COO)
24H
21.5 times of O mole), the capacity that then is transferred to is in 100 milliliters the autoclave (compactedness 80%, percent by volume), then with the reactor sealing, 200 ℃ of lower reactions 30 hours, then to naturally cool to room temperature; Collect solid reaction product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, 60 ℃ of lower vacuumizes obtain 0.78g NiS thin slice/graphene composite material with product, and wherein, the weight percentage of Graphene is 7.4%.
Be NiS thin slice/graphene composite material from the X ray diffracting spectrum of the composite material of gained and the composite material that transmission electron microscope photo can be found out gained, wherein NiS is laminar, and lamina dimensions is 200 nanometers~500 nanometers, and it is more even to distribute.
Comparative Examples 7
Adopt the method preparation among the Chinese patent application CN201210254567.2, specific as follows:
Except not adding the trisodium citrate, all the other operate with embodiment 4, make 0.75g NiS particle/graphene composite material, and wherein, the weight percentage of Graphene is 8.5%.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the composite material of gained the composite material of gained is NiS particle/graphene composite material, wherein NiS is graininess, and particle size is 50 nanometers~100 nanometers, and it is more even to distribute.
Comparative Examples 8
Except not adding the GO, all the other operate with embodiment 4, make the pure nanometer NiS particle of 0.64g.
Can find out that from X ray diffracting spectrum and the transmission electron microscope photo of the pure nanometer NiS particle of gained the product of gained is pure nanometer NiS particle, wherein NiS is graininess, and particle size is 100 nanometers~150 nanometers, and size is more even.
Four, performance test
The pure nanometer NiS particle of the NiS particle for preparing with embodiment 4 gained NiS thin slice/G composite materials, Comparative Examples 7 respectively/G composite material and Comparative Examples 8 preparations carries out electrochemical property test as lithium ion battery negative material, constant current charge-discharge (current density 50mAg
-1, voltage range 0.005~3V) test shows that cycle-index is at 1 o'clock, the capacity of NiS thin slice/G composite material is 795mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS thin slice/G composite material only is reduced to 593mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nanometer NiS particle is 575mAhg
-1, cycle-index is 35 o'clock, it only is 55mAhg that the capacity of pure nanometer NiS particle reduces rapidly
-1Cycle-index is 1 o'clock, and the capacity of NiS particle/G composite material is 715mAhg
-1, cycle-index is 35 o'clock, the capacity of NiS particle/G composite material comparatively fast is reduced to 389mAhg
-1As seen compare with pure nanometer NiS particle, NiS particle/G composite material, the cyclical stability of NiS thin slice/G composite material obviously improves, and electrochemical stability is good.
Simultaneously, comparative example 4 and Comparative Examples 7, Comparative Examples 8 also can be found out, if do not use simultaneously graphene oxide and surfactant can't obtain laminar NiS.
Claims (10)
1. a nickel sulfide thin slice/graphene composite material is comprised of nanoscale nickel sulfide and Graphene, it is characterized in that, described nanoscale nickel sulfide is flaky texture.
2. nickel sulfide thin slice/graphene composite material according to claim 1 is characterized in that, the weight percentage of Graphene is 0.4%~20% in the described composite material.
3. nickel sulfide thin slice/graphene composite material according to claim 1 is characterized in that, described nickel sulfide thin slice is of a size of 100 nanometers~500 nanometers.
4. nickel sulfide thin slice/graphene composite material according to claim 3 is characterized in that, described nickel sulfide thin slice is of a size of 200 nanometers~500 nanometers.
5. nickel sulfide thin slice/graphene composite material according to claim 1 is characterized in that, nanoscale nickel sulfide thin slice is Uniform Dispersion in the described composite material.
6. the preparation method of each described nickel sulfide thin slice/graphene composite material according to claim 1~5 may further comprise the steps:
1) hydrate with nickeliferous salt or nickeliferous salt is dissolved in deionized water or the organic solvent, obtains with nickel ion Ni
2+Meter concentration is the solution of 0.01mol/L~0.1mol/L, adds graphene oxide again, through fully obtaining mixed solution after the dispersed with stirring;
The addition of described graphene oxide is 1%~50% of nickel sulfide theoretical weight;
2) add sulfur-containing compound in the mixed solution with step 1), addition is 2 times~4 times of salt mole nickeliferous in the step 1), the hydrate that adds again surfactant trisodium citrate or trisodium citrate, described surfactant addition is 1 times~3 times of salt mole nickeliferous in the step 1), be warming up to 160 ℃~240 ℃ after the sealing, react cooling after 12 hours~48 hours, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains nickel sulfide thin slice/graphene composite material.
7. preparation method according to claim 6 is characterized in that, the nitrate of the chloride that described nickeliferous salt is nickel, the fluoride of nickel, nickel, the sulfate of nickel, the oxalates of nickel or the acetate of nickel.
8. preparation method according to claim 6 is characterized in that, described sulfur-containing compound is vulcanized sodium, potassium sulfide, ammonium sulfide, sodium thiosulfate, potassium thiosulfate, ATS (Ammonium thiosulphate), thiopropionamide, thioacetamide, thiocarbamide or carbon disulfide.
9. preparation method according to claim 6 is characterized in that, described organic solvent is ethanol, methyl alcohol, ethylene glycol, n-butyl alcohol, DMF, pyridine, ethylenediamine, benzene or toluene.
10. according to claim 1,2,3,4 or 5 described nickel sulfide thin slice/graphene composite materials are as the application in the lithium ion battery negative material.
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