CN108807835A - The preparation method and battery of one type of metal graphene negative material - Google Patents
The preparation method and battery of one type of metal graphene negative material Download PDFInfo
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Abstract
The invention discloses the preparation methods and battery of a type of metal graphene negative material, wherein the described method comprises the following steps：Prepare graphene oxide；The graphene oxide being prepared and ammonium molybdate are subjected to mixed processing；The 1T-MoS with layering three-dimensional structure is prepared in mixture progress hydro-thermal reaction2/ graphene composite material.Its described 1T-MoS2/ graphene composite material is atom level and interface three layers of nanostructure of good sandwich-like；The 1T-MoS2/ graphene composite material is ultra-thin two-dimension lamellar graphite alkene piece/two dimension 1T-MoS of vertical stacking2It is layered dissimilar materials.The 1T-MoS2/ graphene composite material has very high reversible capacity, the cycle life of overlength, excellent coulombic efficiency and higher high rate performance as lithium/sodium-ion battery and lithium/sodium Dual-ion cell negative material.
Description
Technical field
The present invention relates to the preparation method of the technical fields such as battery more particularly to a type of metal graphene negative material and
Battery.
Background technology
Since traditional fossil energy constantly consumes and serious Global Environmental Problems, exploitation green and sustainable energy day
Benefit is important.Current such as metal ion battery, metal-air battery, metal sulfide battery and Dual-ion cell etc. be various have it is uncommon
The energy storage device of prestige is invented.And it has been devoted to grinding to the electrode material with high power capacity and superior electrical conductivity
Study carefully, to replace state-of-the-art graphite cathode material at present, because of low (the 372mAh g of graphite cathode material theoretical capacity-1) and it is reversible
Capacity is limited.Molybdenum disulfide (MoS2) it is a kind of typical inexpensive two-dimensional material, because of MoS2With stratiform identical with graphite
Structure and high lithium/sodium storage volume (670mAhg-1).However, MoS2Electric conductivity it is too low.Meanwhile it being circulated throughout in battery charging and discharging
Cheng Zhongqi has accumulated a large amount of strain.These all hinder its application in energy storage field.
A large amount of research is carried out at present to improve MoS2The chemical property of electrode, such as synthesize nanostructure
MoS2With with conducting polymer or carbon combination MoS2Form nanocomposite.However, these are based on MoS2Nanocomposite
Conductivity it is still very low.Therefore, it is highly desirable novel MoS of the exploitation with superior electrical conductivity2Based nano composite material.It is many
It is well known, 1T-MoS2It is metal, there is excellent electric conductivity (107 times higher than 2H phases).Therefore, 1T-MoS2It is potentially good
Candidate material.
Invention content
To solve the problems such as graphite cathode capacity existing for current lithium/sodium-ion battery, lithium/sodium Dual-ion cell is relatively low.
The present invention provides the preparation method and battery of a type of metal graphene negative material, 1T-MoS2/ graphene composite material is
Atom level and interface three layers of nanostructure of good sandwich-like；The 1T-MoS2/ graphene composite material is the super of vertical stacking
Thin two-dimensional layer graphene film/two dimension 1T-MoS2It is layered dissimilar materials.The 1T-MoS2/ graphene composite material is as lithium/sodium
Ion battery and lithium/sodium Dual-ion cell negative material have very high reversible capacity, the cycle life of overlength, excellent coulomb
Efficiency and higher high rate performance.
To achieve the above object, the present invention uses following technical scheme, the preparation of a type of metal graphene negative material
Method includes the following steps：
Prepare graphene oxide；
The graphene oxide being prepared and ammonium molybdate are subjected to mixed processing；
The 1T-MoS with layering three-dimensional structure is prepared in mixture progress hydro-thermal reaction2/ graphene composite material.
Further, described to prepare graphene oxide specifically comprising step：By dense H2SO4And H3PO4It is mixed；By stone
Ink powder and KMnO4Uniformly mixing；By the dense H of 100-200mL2SO4/H3PO4Graphite powder and KMnO is added in mixed solution4Mixture
In；It is then heated to 40-80 DEG C and continues to stir lower 10-24h；Reaction solution is poured into the ice water of 100-300mL again, then
Hydrogen peroxide is added dropwise dropwise into solution, until solution colour becomes golden yellow；Then by mixture in rotating speed 3000-5000rpm
Lower centrifugation 20-60min；Gained mixture is washed with deionized, and is extracted in ethanol；Finally extract is freeze-dried
Graphene oxide is obtained after 20-30h.
Further, the dense H2SO4And H3PO4According to volume ratio 5-10：1 is mixed.
Further, the graphite powder and potassium permanganate are 1 according to mass ratio:5-10 is mixed.
Further, described to be specially by the graphene oxide being prepared and ammonium molybdate progress mixed processing：First will
Ammonium molybdate and thiocarbamide are uniformly mixed；Then the aqueous solution of 10-30mL is added；20-50mg is finally added into mixed liquor
Graphene oxide is stirred until solution colour brightens.
Further, the mass ratio of the ammonium molybdate and thiocarbamide is 1：10-50.
Further, described to be specially by mixture progress hydro-thermal reaction：Mixture is transferred to Teflon liner not
It becomes rusty in steel autoclave, then continuous heating reacts 20-30h at 200-300 DEG C, obtains the 1T- with layering three-dimensional structure
MoS2/ graphene composite material.
The invention also discloses a kind of lithium ion battery, negative material is using any of the above-described 1T-MoS2/ graphite
Alkene composite material.
A kind of preparation method of cell negative electrode material, by any of the above-described 1T-MoS2/ graphene composite material and
Acetylene black and carboxymethyl group cellulose are 1-8 in mass ratio：1：1 is mixed, and it is 1 to be then dissolved in mass ratio：1-2.5
C2H5OH and H2In the solution of O, and mixture is dried after continuing stirring, cell negative electrode material is made.
The present invention uses above technical scheme, the metalloid 1T-MoS being prepared2/ graphene composite material is led with height
Electrically with relatively rich layer structure nano channel, have as the negative material of lithium/sodium-ion battery and lithium/sodium Dual-ion cell
It has the following advantages：
(1) metal phase MoS2High conductivity greatly improve the electric conductivity of electrode, 1T-MoS2Between graphene
Close coupling can realize the rapid electric charge transfer of electrode and good structural stability；
(2)1T-MoS2/ graphene composite material inner porosity provides advantageous ring for the diffusion of electrolyte ion
Border；
(3)MoS2Close contact surface between graphene, which can be reduced, to be rearranged, and can effectively be buffered aobvious
The volume change of work, to which cycle can be stablized under relatively high sweep speed.
(4) 1T-MoS2/ graphene composite negative poles show excellent chemical property, that is, have very high reversible
Capacity, the cycle life of overlength, low electrode current potential and excellent coulombic efficiency and high rate performance.
Description of the drawings
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
Example and its explanation are applied for explaining the present invention, is not constituted improper limitations of the present invention.In the accompanying drawings：
Fig. 1 is 1T-MoS provided by the invention2/ graphene composite material preparation process schematic diagram；
Fig. 2 is 1T-MoS provided by the invention2/ graphene composite material hydro-thermal reaction building-up process schematic diagram；
Fig. 3 is 1T-MoS provided by the invention2The SEM photograph of/graphene composite material；
Fig. 4 is 1T-MoS provided by the invention2The TEM photos of/graphene composite material；
Fig. 5 is 1T-MoS provided by the invention2Electrification of/the graphene composite material as the lithium ion battery of negative material
Performance map is learned, wherein (A) figure is first three circle cyclic voltammetry curve figure under 0.5mV/S sweep speeds；(B) figure is in 1A/g electricity
Constant current charge-discharge curve under current density；(C) figure is the cyclic curve figure under 1A/g current densities；
Fig. 6 is the high rate performance curve graph of lithium ion battery provided by the invention；
Fig. 7 is cyclic curve figure of the lithium ion battery provided by the invention under 10A/g current densities.
Fig. 8 is 1T-MoS provided by the invention2Electrification of/the graphene composite material as the sodium-ion battery of negative material
Performance map is learned, wherein first three the circle cyclic voltammetry curve figure of (A) figure under 0.5mV/S sweep speeds；(B) figure is in 200mA/ electricity
Constant current charge-discharge curve under current density；(C) figure is the cyclic curve figure under 200mA/g current densities；
Fig. 9 is that graphite provided by the invention and 1T-MoS2/ graphene composite materials are double respectively as the lithium of positive and negative pole material
The chemical property figure of ion battery, wherein first three the circle cyclic voltammetry curve figure of (A) figure under 0.5mV/S sweep speeds；(B)
Figure is the constant current charge-discharge curve under 1A/g current densities；(C) figure is the cyclic curve figure under different current densities；
Figure 10 is the sodium of graphite provided by the invention and 1T-MoS2/ graphene composite materials respectively as positive and negative pole material
The chemical property figure of Dual-ion cell, wherein (A) figure is first three circle cyclic voltammetry curve under 0.5mV/S sweep speeds
Figure；(B) figure is the constant current charge-discharge curve under 200mA/g current densities；(C) figure is that the cycle under different current densities is bent
Line chart；
Figure 11 is lithium provided by the invention/sodium Dual-ion cell charge and discharge process schematic diagram.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The present invention provides the preparation methods and battery of a type of metal graphene negative material.The 1T-MoS2/ graphite
Alkene composite material is atom level and interface three layers of nanostructure of good sandwich-like；The 1T-MoS2/ graphene composite material is
Ultra-thin two-dimension lamellar graphite alkene piece/two dimension 1T-MoS of vertical stacking2It is layered dissimilar materials.The 1T-MoS2/ graphene is compound
Material has very high reversible capacity, the cycle longevity of overlength as lithium/sodium-ion battery and lithium/sodium Dual-ion cell negative material
Life, excellent coulombic efficiency and high rate performance.Hydrothermal reaction process mechanism of the present invention, first in initial reaction stage, due to carboxyl and
The ionization of phenolic hydroxyl group, the surface of graphene oxide is usually negatively charged in aqueous solution, so while electrostatic repulsion,
Mo7o24 6-It is difficult to be combined in surface of graphene oxide with the sources Mo.Therefore Mo7o24 6-Precursor liquid is by excessive thiocarbamide (CN2H4S) also
Original forms the 1T MoS of multilayer2；Graphene oxide film is reduced into redox graphene (RGO) simultaneously.Because lamella it
Between the Van der Waals force that interacts so that MoS2More easily epitaxial growth on the surface of graphene, so in hydrothermal reaction process
Form the 1TMoS of layering three-dimensional structure2/ graphene composite material.
As shown in Figure 1,1T-MoS provided by the invention2/ graphene composite material preparation method is as follows：
S01：Prepare graphene oxide；First, by H2SO4And H3PO45-10 by volume：1 is mixed to get dense H2SO4/
H3PO4Mixed liquor；By graphite powder and potassium permanganate (KMnO4) in mass ratio 1：5-10 is uniformly mixed；Then 100-200mL is dense
H2SO4/H3PO4Graphite powder and KMnO is added in mixed solution4Mixture in；It is then heated to 40-80 DEG C and continues to stir lower 10-
24h；Reaction solution is poured into the ice water of 100-300mL again, then 30% hydrogen peroxide is added dropwise dropwise into solution, is added drop-wise to solution
Color becomes golden yellow；Then mixture is centrifuged into 20-60min at rotating speed 3000-5000rpm, gained mixture spend from
Sub- water washing, and extract in ethanol；Graphene oxide (GO) is obtained after extract is finally freeze-dried 20-30h.
S02：Graphene oxide and ammonium molybdate mixed processing；First by ammonium molybdate ((NH4)6Mo7O24·4H2) and thiocarbamide O
(CN2H4S it is) 1 in mass ratio：10-50 is uniformly mixed；Then the aqueous solution mixing of 10-30mL is added；Last past mixed liquor
The middle graphene oxide that 20-50mgS01 steps are added and obtain, is stirred until solution colour brightens；
S03：Hydro-thermal reaction；The obtained suspension of step S02 is transferred in the stainless steel autoclave of Teflon liner, so
Continuous heating reacts 20-30h at 200-300 DEG C afterwards, obtains 1T MoS2/ graphene composite material.Wherein, hydro-thermal reaction mistake
Journey mechanism is as shown in Fig. 2, i.e. first in initial reaction stage, due to the ionization of carboxyl and phenolic hydroxyl group, graphite oxide in aqueous solution
The surface of alkene is usually negatively charged, so while electrostatic repulsion, Mo7o24 6-It is difficult in surface of graphene oxide knot with the sources Mo
It closes.Therefore Mo7o24 6-Precursor liquid is by excessive thiocarbamide (CN2H4S it) restores, forms the 1T MoS of multilayer2；Simultaneously by graphene oxide
Film is reduced into redox graphene (RGO).Because of the Van der Waals force to interact between lamella so that MoS2More easily exist
Graphene surface epitaxial growth, so foring the 1TMoS of layering three-dimensional structure in hydrothermal reaction process2/ graphene is compound
Material.
The specific present invention may be used following implementation and implement：
Embodiment 1
Prepare graphene oxide：By H2SO4And H3PO4By volume 9：1 carries out being mixed to get dense H2SO4/H3PO4Mixed liquor；
By 1.5g graphite powders and 9g potassium permanganate (KMnO4) uniformly mixing；Then by the dense H of 180mL2SO4/H3PO4Stone is added in mixed solution
Ink powder and KMnO4Mixture in；Then 50 DEG C are heated the mixture to and continues to stir lower 20h；Reaction solution is poured into again
In the ice water of 200mL, then 30% hydrogen peroxide is added dropwise dropwise into solution, being added drop-wise to solution colour becomes golden yellow；Then it will mix
It closes object and centrifuges 30min at rotating speed 4000rpm, gained mixture is washed with deionized, and extracts in ethanol；It finally will extraction
Object freeze-drying is taken to obtain graphene oxide (GO) afterwards for 24 hours.
Graphene oxide and ammonium molybdate mixed processing：First by 60mg ammonium molybdates ((NH4)6Mo7O24·4H2) and 1.5g sulphur O
Urea (CN2H4S it) is uniformly mixed；Then the aqueous solution mixing of 10mL is added；30mgS01 steps are finally added into mixed liquor
Obtained graphene oxide is stirred until solution colour brightens；
Hydro-thermal reaction：The obtained suspension of step S02 is transferred in the stainless steel autoclave of Teflon liner, is then existed
Continuous heating reaction for 24 hours, obtains 1TMoS at 240 DEG C2/ graphene composite material.
1T-MoS as shown in Figure 3 and Figure 42/ graphene composite material SEM and TEM photos can be seen that oxygen reduction fossil
Black alkene (RGO) sheet material is by several layers of MoS2Covering, forms good conductive structure, and the thickness of graphene nanometer sheet is about several receives
Rice.
The invention also discloses a kind of preparations of battery：
Electrode material is prepared first, by 1T-MoS2/ graphenes negative material and acetylene black and carboxymethyl group cellulose
It is 8 in mass ratio：1：1 is mixed, and C is then dissolved in2H5OH:H2O mass ratioes are 1：In 2.5 solution, and it is small to continue stirring 8
When.Mixture coating is used for thin copper foil, it is then dry in vacuum drying oven at 65 DEG C, as cell negative electrode material；
The weight of wherein 1T-MoS2/ graphenes negative electrode active material is about 1.5mg/cm2；The positive electrode of lithium/sodium-ion battery is distinguished
With lithium piece and sodium piece；1M lithium hexafluoro phosphates are respectively adopted in lithium/sodium-ion battery and 1M sodium hexafluoro phosphates are dissolved in volume ratio for carbonic acid
Sub- diester：Dimethyl carbonate=6：4(EC:DMC=6:4) it is used as electrolyte；And (the H under ar gas environment2O<0.5ppm, O2<
Lithium/sodium ion half-cell is assembled into glove box 0.5ppm).
As shown in Fig. 5 lithium ion battery chemical property curve graphs, it can be seen that from the cyclic voltammetry curve figure of Fig. 5 (A)
The reduction peak and oxidation peak of the 1T-MoS2/ Graphene electrodes of lithium ion battery are nearly all reversible, this is primarily due to electrode
The raising of material electric conductivity effectively reduces inside battery electrochemistry resistance.From Fig. 5 (B) it can be seen that the high current in 1A/g is close
The lower charge and discharge cycles of degree, have obtained the superelevation discharge capacity of 1200mAh/g and 60% Initial Coulombic Efficiencies.It can be with from Fig. 5 (C)
Find out the coulomb effect that 600 capacity holdings for still having 1100mAh/g and each charge and discharge cycles are recycled under 1A/g current densities
Rate illustrates that its stable circulation performance is good all close to 100%.It can be seen that from lithium ion battery high rate performance curve shown in fig. 6
When current density progressively increases to 10A/g from 0.1A/g, the charging and discharging curve under each current density can stablize holding, and
The reversible capacity that 750mAh/g is still kept under the high current density of 10A/g, 64% capacity being equivalent under 0.1A/g.And work as
Battery capacity rapidly increases to about 1150mAh/g when current density drops to 0.1A/g, illustrates that capacity restoration is good, high rate performance
It is good.Even battery also shows excellent stable circulation performance under the high current density of 10A/g as can be seen from Figure 7.
As shown in Fig. 8 sodium-ion battery chemical property curve graphs, it can be seen that from the cyclic voltammetry curve figure of Fig. 8 (A)
The volt-ampere curve of first cycle shows in 0.2V and mainly reduces sharply peak, and the peak value of the 0.6V of 2H-1T phase transformations may be not present, this into
One step demonstrates MoS prepared by the present invention2It is 1T phases.From Fig. 8 (B) it can be seen that the charge and discharge under 200mA/g current densities
Cycle, each provides the charging and discharging capacity of 800mAh/g and 600mAh/g, cycle coulombic efficiency immediate stability later
98% or so.Still there is the capacity of 480mAh/g to protect from Fig. 8 (C) it can be seen that recycling 100 times under 200mA/g current densities
It holds.
Embodiment 2
Prepare graphene oxide：First, by H2SO4And H3PO4By volume 9：1 carries out being mixed to get dense H2SO4/H3PO4It is mixed
Close liquid；By 2g graphite powders and 10g potassium permanganate (KMnO4) uniformly mixing；Then by the dense H of 180mL2SO4/H3PO4Mixed solution adds
Enter graphite powder and KMnO4Mixture in；Then 55 DEG C are heated the mixture to and continues to stir lower 22h；Again by reaction solution
It pours into the ice water of 200mL, then 30% hydrogen peroxide is added dropwise dropwise into solution, being added drop-wise to solution colour becomes golden yellow；Then
Mixture is centrifuged into 60min at rotating speed 4000rpm, gained mixture is washed with deionized, and extracts in ethanol；Finally
Extract freeze-drying is obtained into graphene oxide (GO) afterwards for 24 hours.
Graphene oxide and ammonium molybdate mixed processing：First by 60mg ammonium molybdates ((NH4)6Mo7O24·4H2) and 2g thiocarbamides O
(CN2H4S it) is uniformly mixed；Then the aqueous solution mixing of 15mL is added；35mgS01 steps are finally added into mixed liquor to obtain
The graphene oxide arrived is stirred until solution colour brightens；
Hydro-thermal reaction：The obtained suspension of step S02 is transferred in the stainless steel autoclave of Teflon liner, is then existed
Continuous heating reacts 28h at 240 DEG C, obtains 1TMoS2/ graphene composite material.
It is prepared by lithium/sodium Dual-ion cell：Positive and negative electrode material is prepared first, by 1T-MoS2/ graphene negative material (stones
Black positive electrode)：Acetylene black：Carboxymethyl group cellulose is 8 in mass ratio：1：1 is mixed, and C is then dissolved in2H5OH:H2O
Mass ratio is 1：In 2.5 solution, and continue stirring 8 hours.Mixture is respectively coated for 1T-MoS2/ graphene cathode
Thin copper foil and aluminium foil for graphite anode, it is then dry in vacuum drying oven at 65 DEG C.Wherein 1T-MoS2/ graphite
The weight of alkene negative electrode active material is about 1.5mg/cm2, positive graphite is 3mg/cm2, 1M is respectively adopted in lithium/sodium Dual-ion cell
It is carbonic acid Asia diester that lithium hexafluoro phosphate and 1M sodium hexafluoro phosphates, which are dissolved in volume ratio,：Dimethyl carbonate=6：4(EC:DMC=6:4) make
For electrolyte, and (the H under ar gas environment2O<0.5ppm, O2<Lithium/sodium Dual-ion cell is assembled into glove box 0.5ppm).
It can be seen that from Fig. 9 lithium Dual-ion cell chemical properties and be clearly visible charging in 9 (A) cyclic voltammetry curves
Occur peak value near 3.25V in the process, and other two peak value occurs in about 3.4V and 4.4V in discharge process.9 (B's)
Typical charge and discharge curve shows that the charging and discharging capacity of lithium Dual-ion cell is respectively 500mAh/g and 360mAh/g.9 (C) batteries
High rate performance is carried out in various current densities, it can be seen that it is relatively high to provide 400mAh/g under 200mA/g current densities
Capacity；And coulombic efficiency reaches 90% or so when current density is increased to 500mA/g.Lithium Dual-ion cell 200,400,
The capacity that 420,380,360,340 and 330mAh/g are each provided under 600,800 and 1000mA/g current densities, shows excellent
High rate performance more.
It can be seen that be clearly visible in 10 (A) cyclic voltammetry curves from Figure 10 sodium Dual-ion cell chemical properties and fill
Occur peak value in electric process near 3.25V, and other two peak value occurs in about 3.4V and 4.4V in discharge process.9(B)
Typical charge and discharge curve show lithium Dual-ion cell charging and discharging capacity be respectively 500mAh/g and 360mAh/g.9 (C) electricity
Pond high rate performance is carried out in various current densities, it can be seen that it is relatively high to provide 400mAh/g under 200mA/g current densities
Capacity；And coulombic efficiency reaches 90% or so when current density is increased to 500mA/g.Lithium Dual-ion cell 200,400,
The capacity that 420,380,360,340 and 330mAh/g are each provided under 600,800 and 1000mA/g current densities, shows excellent
High rate performance more.
Metalloid 1T-MoS provided by the invention2/ graphene composite material has high conductivity and relatively rich layer structure
Nanochannel, 1TMoS2Close coupling between graphene can realize the rapid electric charge transfer of electrode and good stable structure
Property；Its inner porosity provides advantageous environment for the diffusion of electrolyte ion simultaneously；In addition MoS2Between graphene
Close contact surface can reduce and rearrange, and can effectively buffer the significant volume change of charge and discharge process；It is made
For the negative material of lithium/sodium-ion battery and lithium/sodium Dual-ion cell, with very high reversible capacity, overlength cycle life,
Low electrode current potential and excellent coulombic efficiency and high rate performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. the preparation method of a type of metal graphene negative material, which is characterized in that include the following steps：
Prepare graphene oxide；
The graphene oxide being prepared and ammonium molybdate are subjected to mixed processing；
The 1T-MoS with layering three-dimensional structure is prepared in mixture progress hydro-thermal reaction2/ graphene composite material.
2. the preparation method of metalloid graphene negative material according to claim 1, it is characterised in that：It is described to prepare oxygen
Graphite alkene includes specifically step：By dense H2SO4And H3PO4It is mixed；By graphite powder and KMnO4Uniformly mixing；By 100-
The dense H of 200mL2SO4/H3PO4Graphite powder and KMnO is added in mixed solution4Mixture in；It is then heated to 40-80 DEG C and continues
The lower 10-24h of stirring；Reaction solution is poured into the ice water of 100-300mL again, hydrogen peroxide is then added dropwise dropwise into solution, directly
Become golden yellow to solution colour；Then mixture is centrifuged into 20-60min at rotating speed 3000-5000rpm；Gained is mixed
Object is washed with deionized, and extracts in ethanol；Graphene oxide is obtained after extract is finally freeze-dried 20-30h.
3. the preparation method of metalloid graphene negative material according to claim 2, it is characterised in that：The dense H2SO4
And H3PO4According to volume ratio 5-10：1 is mixed.
4. the preparation method of metalloid graphene negative material according to claim 1, it is characterised in that：The graphite powder
It is 1 with potassium permanganate installation quality ratio:5-10 is mixed.
5. the preparation method of metalloid graphene negative material according to claim 1, it is characterised in that：It is described to prepare
Obtained graphene oxide carries out mixed processing with ammonium molybdate：Ammonium molybdate and thiocarbamide are uniformly mixed first；So
The aqueous solution of 10-30mL is added afterwards；20-50mg graphene oxides are finally added into mixed liquor, are stirred until solution
Bright color.
6. the preparation method of metalloid graphene negative material according to claim 1, it is characterised in that：The ammonium molybdate
Mass ratio with thiocarbamide is 1：10-50.
7. the preparation method of metalloid graphene negative material according to claim 1, it is characterised in that：It is described to mix
Object carries out hydro-thermal reaction：Mixture is transferred in the stainless steel autoclave of Teflon liner, then at 200-300 DEG C
Lower continuous heating reacts 20-30h, obtains the 1T-MoS with layering three-dimensional structure2/ graphene composite material.
8. a kind of battery, it is characterised in that：It includes any 1T-MoS of claim 1-7 that its negative material, which uses,2/ graphite
Alkene composite material.
9. a kind of preparation method of cell negative electrode material, it is characterised in that：It is by any 1T-MoS of claim 1-72/
Graphene composite material and acetylene black and carboxymethyl group cellulose are 1-8 in mass ratio：1：1 is mixed, and is then dissolved in
Mass ratio is 1：The C of 1-2.52H5OH and H2In the solution of O, and mixture is dried after continuing stirring, battery cathode material is made
Material.
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