CN105789592B - Surface is loaded with three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three and its preparation method and application - Google Patents
Surface is loaded with three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of three-dimensional grapheme combination electrode, using three-dimensional porous foams nickel as matrix, direct growth graphene on matrix, direct growth flower-shape Ni on described graphene3S2.The invention also discloses the preparation method and application of described three-dimensional grapheme combination electrode.Described preparation method, have technique is simple, cost is low, the cycle is short, low power consumption and other advantages, be adapted to large-scale industrial production；The three-dimensional grapheme based combined electrode being prepared is free of any conductive agent and binding agent, due to special three-dimensional porous structure and flower-shape Ni3S2With the conduction and fixation of graphene, when described combination electrode is used for sodium-ion battery, higher capacity and preferable cyclical stability are shown.
Description
Technical field
The present invention relates to sodium-ion battery combination electrode field, and in particular to a kind of three-dimensional grapheme combination electrode and its
Preparation method and application.
Background technology
Lithium ion battery is widely used as mobile electronic device, such as smart mobile phone, notebook computer, and in electricity now
Net energy storage, electric automobile field have huge market.But with the popularization of lithium ion battery, particularly in electric automobile
Upper large-scale use, the consumption of lithium resource is also huge.And the reserves of lithium resource are limited, and at present to discarded lithium from
The recovery of elemental lithium lacks effective, economic technology in sub- battery.By contrast, the reserves of sodium element on earth are much high
In elemental lithium, price is also far below lithium.Therefore, in recent years, sodium-ion battery is paid attention to extensively.It is generally believed that sodium ion is electric
Pond has tempting prospect in power network energy storage field.
Traditional lithium ion battery uses graphite as negative pole, but because the radius of sodium ion is much larger than lithium ion, sodium from
Son is difficult to be embedded between graphite linings.Therefore, the storage sodium capacity of graphite is far below lithium storage content, generally below 300mAh/g.Mirror
In this, exploitation novel high-capacity stores up the key factor that sodium negative material is researched and developed into sodium-ion battery.It is embedded in relative to sodium ion
Reversible conversion reaction can occur for the graphite type material of mechanism, some sulfide and sodium, the corresponding higher storage sodium of the storage sodium mechanism
Capacity.As following reaction can occur for NiS and Na：The theoretical storage sodium capacity of the reaction is up to
590mAh/g。
Although sulfide has higher storage sodium activity, because sulfide electrical conductivity is relatively low, influences it and store up sodium activity
Play, it is necessary to add conductive carbon to improve the conductance of electrode.In addition, for traditional coating processes, generally require to polymerize
Thing binding agent fixes active particle.
By the way that active material is directly grown on conducting base, electrical conductivity on the one hand can be improved, the opposing party can avoid
Use polymeric binder.Graphene is non-convention because its high electrical conductivity, high mechanical strength, big specific surface area agent
The matrix material thought.Conductive and fixation can be met simultaneously using graphene as matrix, in sodium-ion battery electrode design
It is upper that there is good prospect, but there is presently no the document report of this respect.
The content of the invention
The invention provides a kind of three-dimensional grapheme combination electrode for sodium-ion battery and its preparation method and application.
Preparation technology is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production；The three-dimensional grapheme compound electric being prepared
Have high power capacity and high circulation stability, be applied in sodium-ion battery electrode, can be used to improve sodium-ion battery
Chemical property, particularly improve capacity and cyclical stability.
The preparation method of the three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three is loaded with the invention discloses a kind of surface,
Comprise the following steps：
1) using three-dimensional porous foams nickel as matrix, by chemical vapour deposition technique, graphene is directly grown on matrix, is remembered
For Ni/G；
2) thiocarbamide and anhydrous sodium sulfate are dissolved in deionized water, are uniformly mixing to obtain mixed solution, in the mixed solution
SO4 2–Concentration is 0.01~0.05mol/L；
The mol ratio of the thiocarbamide and anhydrous sodium sulfate is 0.2~1.0；
3) mixed solution for obtaining the Ni/G immersions step 2) that step 1) obtains, through 100~150 DEG C of hydro-thermal reactions 1~
Surface must be arrived after 5h, then scrubbed, drying and is loaded with the Ni/G for being loaded with the nickel of curing three, be designated as Ni/G/Ni3S2。
The present invention directly prepares graphene, described stone by CVD using three-dimensional porous foams nickel as matrix on matrix
Black alkene replicates the three-dimensional porous structure of nickel foam；Again by hydro-thermal method in three-dimensional grapheme surface direct growth flower-shape Ni3S2。
Graphene serves double action, not only Ni3S2Electric action is provided, and flower-shape Ni can be fixed3S2, so as to improve its appearance
Amount and cyclical stability.
Described direct growth refers to：First by CVD, directly graphene is prepared on the skeleton of nickel foam；Then
Under hydrothermal conditions, flower-shape Ni3S2It is directly grown on graphene；In contrast, indirect growth refers to pre-synthesis graphene
And flower-shape Ni3S2, then two kinds of raw materials and binding agent are well mixed in organic solvent, stir into slurry, then it is coated in bubble
On foam Ni substrate.
Preferably, in step 1), chemical vapor deposition concretely comprises the following steps：
Three-dimensional porous foams nickel is placed in reactor, is warming up to 800~1200 DEG C, after insulation under an ar atmosphere, then draw
Enter methane, room temperature is cooled to after reaction.
Preferably, three-dimensional porous foams nickel is put into tube furnace, 1000 DEG C, after insulation are warming up under an ar atmosphere,
Methane is introduced in quartz ampoule with Ar air-flows again, reacts 3~10min；Finally, room temperature is cooled under an ar atmosphere, is grown
Three-dimensional grapheme on nickel foam substrate；It is designated as Ni/G.
Preferably, in step 3), described hydrothermal temperature is 110~130 DEG C.
The temperature of described cooling does not have strict restriction, based on adequate operation, can typically be cooled to 15~30 DEG C
Environment temperature.
The invention also discloses the three-dimensional grapheme that the flower-shaped nickel of curing three is loaded with according to the surface of above-mentioned method preparation
Combination electrode, described three-dimensional grapheme combination electrode material is using three-dimensional porous foams nickel as matrix, direct growth stone on matrix
Black alkene, the flower-shaped nickel of curing three of direct growth on described graphene, is designated as Ni/G/Ni3S2。
Ni in the present invention3S2Come from metallic nickel, therefore the nickel of flower-shaped curing three is necessarily connected with metallic nickel matrix.Separately
Outside, due in Ni3S2Graphene, Ni are grown before growth in advance3S2Nanometer sheet necessarily runs through graphene sheet layer, therefore flower-shaped
Ni3S2Graphene sheet layer can be run through and by UNICOM of graphene sheet layer institute.Therefore, the performance and machine that the combination electrode has necessarily had
Tool performance.
Flower-shape Ni3S2With less size and higher specific surface area, be advantageous to by electrolyte wetting and material activity
Improve.Preferably, the flower-shape Ni3S2By circular Ni3S2Thin slice forms, monolithic Ni3S2A diameter of 2~3 μm, monolithic Ni3S2
Thickness be only 100~200nm.Relatively thin monolithic Ni3S2Be advantageous to the diffusion of sodium ion, so as to improve the activity of material.
Preferably, in described three-dimensional grapheme combination electrode material the bearing capacity of the flower-shaped nickel of curing three for 0.8~
1.5mg/cm2.Flower-shape Ni3S2Bearing capacity it is very few, the capacity of electrode is with regard to relatively low；Bearing capacity is excessive, and material is not easy to be moistened by electrolyte
Wet, graphene can weaken to it conduction and fixation.
Preferably, the bearing capacity of graphene is 0.3~0.6mg/cm2, graphene plays conductive and fixed in the electrodes
Effect, the mechanical stability of the too low raising and electrode for being unfavorable for electric conductivity of graphene content, and too high content is to conduction
The effect unobvious of the raising of performance and mechanical performance.Therefore, it is the content control of graphene is more reasonable within the above range.
The invention also discloses the surface to be loaded with the three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three in sodium ion electricity
Application in pond.
Compared with prior art, the invention has the advantages that：
1st, graphene and flower-shape Ni in three-dimensional grapheme combination electrode prepared by the present invention3S2It is Ni-based to be directly grown in foam
On body, without other conductive agents and binding agent, with technique is simple, cost is low, the cycle is short, energy consumption is low and suitable industrialized production
The advantages that；
2nd, graphene while conduction and fixation are played in the three-dimensional grapheme combination electrode for preparing of the present invention, can improved
The electro-chemical activity and mechanical stability of electrode, so as to improve the capacity of electrode and cyclical stability；
3rd, compared with traditional electrode slurry coating process, this preparation method can keep the original three-dimensional porous knot of nickel foam
Structure, be advantageous to the wetting of electrode and the buffering of stress, so as to improve the cyclical stability of sodium-ion battery.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of three-dimensional grapheme combination electrode surface mass prepared by embodiment 1；
Fig. 2 is Ni/G prepared by embodiment 1 Raman (Raman) spectrogram；
Fig. 3 is the low power stereoscan photograph of three-dimensional grapheme combination electrode prepared by embodiment 1；
Fig. 4 is the high power stereoscan photograph of three-dimensional grapheme combination electrode prepared by embodiment 1；
Fig. 5 be respectively using embodiment 1 prepare three-dimensional grapheme combination electrode as positive pole, metallic sodium be negative pole assembling sodium
The cyclical stability (a) of ion battery, and using comparative example 1 prepare electrode as positive pole, metallic sodium be negative pole assembling sodium ion
The cyclical stability (b) of battery.
Embodiment
Embodiment 1
Nickel foam is put into tube furnace, with 100 DEG C/min of programming rate liter under Ar (500s.c.c.m.) atmosphere
Temperature is to 1000 DEG C；After insulation 5 minutes, methane is introduced in quartz ampoule with Ar (250s.c.c.m.) air-flows, reacted 5 minutes；Most
Afterwards, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, obtains being grown in the three-dimensional stone on nickel foam substrate
Black alkene (Ni/G), wherein the bearing capacity 0.485mg/cm of graphene2；By thiocarbamide 0.4 times of anhydrous sodium sulfate (mole be) and
Anhydrous sodium sulfate is dissolved in deionized water, stirs, and prepares with SO4 2–Count the solution that concentration is 0.03mol/L；Using Ni/G as
Matrix, immerse above-mentioned solution, retransfer in reactor, 3 hours are incubated in 120 DEG C of baking oven after closed, then spend from
Sub- water and absolute alcohol rinse for several times, must be loaded with and be carried on Ni/G to surface after 60 DEG C of baking ovens are dried in vacuo 12 hours
Ni3S2(Ni/G/Ni3S2), wherein Ni3S2Bearing capacity be 1.03mg/cm2。
Fig. 1 is Ni/G/Ni prepared by this implementation3S2The X-ray diffraction spectrum of electrode, the material can be attributed to Ni3S2And graphite
Alkene.
Fig. 2 is the Ni/G prepared Raman spectrum, and stronger 2D peaks show that graphene is a small number of Rotating fields.
Fig. 3 and Fig. 4 is respectively the G/Ni manufactured in the present embodiment being carried in nickel foam3S2The low power and high power of electrode are swept
Electronic Speculum is retouched, it was found from photo, Ni3S2Flower-like structure, flower-shape Ni is presented3S2By circular Ni3S2Thin slice forms, and monolithic thin slice is a diameter of
2 microns~3 microns, thickness is 100~200nm, and uniform load is on three-dimensional grapheme.
With the G/Ni manufactured in the present embodiment being carried in nickel foam3S2As positive pole, using metallic sodium as negative pole, glass fibers
Dimension (trade mark Whatman GF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte,
Battery is assembled in the glove box full of argon gas, carries out charge-discharge test, cycle life curve is as shown such as curve (a) in Fig. 5.
Constant current charge-discharge tests (current density 50mA/g, wherein voltage range 0.005V~3V, capacity and current density
It is based on the weight of the nickel of curing three) show, circulation volume is 453mAh/g first, and by 60 circulations, capacity is maintained at
267mAh/g。
Comparative example 1
Ni3S2Preparation technology it is same as Example 1, difference Ni3S2It is directly grown on Ni substrate, Ni substrate
Upper growth graphene no in advance.Concrete technology is as follows, by thiocarbamide (mole is 0.4 times of anhydrous sodium sulfate) and anhydrous slufuric acid
Sodium is dissolved in deionized water, stirs, and prepares with SO4 2–Count the solution that concentration is 0.03mol/L；By foam nickel sheet (no graphite
Alkene) matrix is used as, above-mentioned solution is immersed, is retransferred in reactor, is incubated 3 hours in 120 DEG C of baking oven after closed, then
Rinsed for several times with deionized water and absolute alcohol, must arrive surface after 60 DEG C of baking ovens are dried in vacuo 12 hours and be loaded with and be carried on Ni
On Ni3S2(Ni/Ni3S2), wherein Ni3S2Bearing capacity be 1.02mg/cm2.X-ray diffraction spectrum shows that gained material is
Ni3S2.Stereoscan photograph shows, Ni3S2Flower-like structure, flower-shape Ni is presented3S2By circular Ni3S2Thin slice forms, and monolithic thin slice is straight
Footpath is 2 microns~3 microns, and thickness is 200~300nm, and uniform load is on three-dimensional grapheme.
With the Ni manufactured in the present embodiment being carried in nickel foam3S2As positive pole, using metallic sodium as negative pole, glass fibre
(trade mark Whatman GF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte,
Battery is assembled in glove box full of argon gas, charge-discharge test is carried out, sees curve (b) in Fig. 5.
Constant current charge-discharge tests (current density 50mA/g, wherein voltage range 0.005V~3V, capacity and current density
It is based on the weight of the nickel of curing three) show, circulation volume is 368mAh/g first, and by 60 circulations, capacity is reduced to
164mAh/g。
Embodiment 2
Nickel foam is put into tube furnace, with 100 DEG C/min of programming rate liter under Ar (500s.c.c.m.) atmosphere
Temperature is to 1000 DEG C；After insulation 5 minutes, methane is introduced in quartz ampoule with Ar (250s.c.c.m.) air-flows, reacted 8 minutes；Most
Afterwards, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, obtains being grown in the three-dimensional stone on nickel foam substrate
Black alkene (Ni/G), wherein the bearing capacity 0.51mg/cm of graphene2；By thiocarbamide (the 0.2 of mole anhydrous sodium sulfate) and anhydrous sulphur
Sour sodium is dissolved in deionized water, stirs, and prepares with SO4 2–Count the solution that concentration is 0.05mol/L；Using Ni/G as matrix, leaching
Enter above-mentioned solution, retransfer in reactor, 4 hours are incubated in 110 DEG C of baking oven after closed, then with deionized water and nothing
Water-alcohol rinses for several times, must be loaded with the Ni being carried on Ni/G to surface after 60 DEG C of baking ovens are dried in vacuo 12 hours3S2(Ni/
G/Ni3S2), wherein Ni3S2Bearing capacity be 0.93mg/cm2.X-ray diffraction spectrum shows that gained material is Ni3S2And graphene.
Ni/G Raman spectrum show that graphene is a small number of Rotating fields.Stereoscan photograph shows, Ni3S2Flower-like structure is presented, it is flower-shaped
Ni3S2By circular Ni3S2Thin slice forms, and a diameter of 2 microns~3 microns of monolithic thin slice, thickness is 100~200nm, and
It is even to be carried on three-dimensional grapheme.
With the G/Ni manufactured in the present embodiment being carried in nickel foam3S2As positive pole, using metallic sodium as negative pole, glass fibers
Dimension (trade mark Whatman GF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte,
Battery is assembled in the glove box full of argon gas, carries out charge-discharge test.
Constant current charge-discharge tests (current density 50mA/g, wherein voltage range 0.005V~3V, capacity and current density
It is based on the weight of the nickel of curing three) show, circulation volume is 461mAh/g first, and by 60 circulations, capacity is maintained at
272mAh/g。
Embodiment 3
Nickel foam is put into tube furnace, with 100 DEG C/min of programming rate liter under Ar (500s.c.c.m.) atmosphere
Temperature is to 1000 DEG C；After insulation 5 minutes, ethanol is introduced in quartz ampoule with Ar (250s.c.c.m.) air-flows, reacted 3 minutes；Most
Afterwards, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, obtains being grown in the three-dimensional stone on nickel foam substrate
Black alkene (Ni/G), wherein the bearing capacity 0.32mg/cm of graphene2；By thiocarbamide (the 0.6 of mole anhydrous sodium sulfate) and anhydrous sulphur
Sour sodium is dissolved in deionized water, stirs, and prepares with SO4 2–Count the solution that concentration is 0.02mol/L；Using Ni/G as matrix, leaching
Enter above-mentioned solution, retransfer in reactor, 2 hours are incubated in 130 DEG C of baking oven after closed, then with deionized water and nothing
Water-alcohol rinses for several times, must be loaded with the Ni being carried on Ni/G to surface after 60 DEG C of baking ovens are dried in vacuo 12 hours3S2(Ni/
G/Ni3S2), wherein Ni3S2Bearing capacity be 1.01mg/cm2.X-ray diffraction spectrum shows that gained material is Ni3S2And graphene.
Ni/G Raman spectrum show that graphene is a small number of Rotating fields.Stereoscan photograph shows, Ni3S2Flower-like structure is presented, it is flower-shaped
Ni3S2By circular Ni3S2Thin slice forms, and a diameter of 2 microns~3 microns of monolithic thin slice, thickness is 100~200nm, and
It is even to be carried on three-dimensional grapheme.
With the G/Ni manufactured in the present embodiment being carried in nickel foam3S2As positive pole, using metallic sodium as negative pole, glass fibers
Dimension (trade mark Whatman GF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte,
Battery is assembled in the glove box full of argon gas, carries out charge-discharge test.
Constant current charge-discharge tests (current density 50mA/g, wherein voltage range 0.005V~3V, capacity and current density
It is based on the weight of the nickel of curing three) show, circulation volume 445 is mAh/g first, and by 60 circulations, capacity is maintained at
254mAh/g。
Embodiment 4
Nickel foam is put into tube furnace, with 100 DEG C/min of programming rate liter under Ar (500s.c.c.m.) atmosphere
Temperature is to 1000 DEG C；After insulation 5 minutes, ethanol is introduced in quartz ampoule with Ar (250s.c.c.m.) air-flows, reacted 10 minutes；Most
Afterwards, room temperature is cooled to 100 DEG C/min of cooling rate under an ar atmosphere, obtains being grown in the three-dimensional stone on nickel foam substrate
Black alkene (Ni/G), wherein the bearing capacity 0.55mg/cm of graphene2；By thiocarbamide (the 0.8 of mole anhydrous sodium sulfate) and anhydrous sulphur
Sour sodium is dissolved in deionized water, stirs, and prepares with SO4 2–Count the solution that concentration is 0.02mol/L；Using Ni/G as matrix, leaching
Enter above-mentioned solution, retransfer in reactor, 4 hours are incubated in 120 DEG C of baking oven after closed, then with deionized water and nothing
Water-alcohol rinses for several times, must be loaded with the Ni being carried on Ni/G to surface after 60 DEG C of baking ovens are dried in vacuo 12 hours3S2(Ni/
G/Ni3S2), wherein Ni3S2Bearing capacity be 1.13mg/cm2.X-ray diffraction spectrum shows that gained material is Ni3S2And graphene.
Ni/G Raman spectrum show that graphene is a small number of Rotating fields.Stereoscan photograph shows, Ni3S2Flower-like structure is presented, it is flower-shaped
Ni3S2By circular Ni3S2Thin slice forms, and a diameter of 2 microns~3 microns of monolithic thin slice, thickness is 100~200nm, and
It is even to be carried on three-dimensional grapheme.
With the G/Ni manufactured in the present embodiment being carried in nickel foam3S2As positive pole, using metallic sodium as negative pole, glass fibers
Dimension (trade mark Whatman GF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte,
Battery is assembled in the glove box full of argon gas, carries out charge-discharge test.
Constant current charge-discharge tests (current density 50mA/g, wherein voltage range 0.005V~3V, capacity and current density
It is based on the weight of the nickel of curing three) show, circulation volume is 464mAh/g first, and by 60 circulations, capacity is maintained at
277mAh/g。
Claims (4)
1. a kind of surface applied to sodium-ion battery is loaded with the three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three, its feature
It is, described three-dimensional grapheme combination electrode is using three-dimensional porous foams nickel as matrix, and direct growth graphene, described on matrix
Graphene on the flower-shaped nickel of curing three of direct growth；The nickel of flower-shaped curing three is connected with metal Ni substrate, and flower-shaped two
Vulcanize three nickel through graphene sheet layer and by UNICOM of graphene sheet layer institute；The described nickel of flower-shaped curing three is by circular Ni3S2It is thin
Piece forms, and a diameter of 2~3 μm of monolithic thin slice, thickness is 100~200nm；
The surface is loaded with the preparation method of the three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three, comprises the following steps：
1) using three-dimensional porous foams nickel as matrix, by chemical vapour deposition technique, stone is directly grown on matrix under an ar atmosphere
Black alkene, is designated as Ni/G；
2) thiocarbamide and anhydrous sodium sulfate are dissolved in deionized water, are uniformly mixing to obtain mixed solution, SO in the mixed solution4 2–
Concentration is 0.01~0.05mol/L；
The mol ratio of the thiocarbamide and anhydrous sodium sulfate is 0.2~1.0；
3) mixed solution for obtaining the Ni/G immersions step 2) that step 1) obtains, through 100~150 DEG C of 1~5h of hydro-thermal reaction, then
The three-dimensional grapheme combination electrode that surface is loaded with the flower-shaped nickel of curing three must be arrived after scrubbed, dry, is designated as Ni/G/Ni3S2。
2. the surface according to claim 1 applied to sodium-ion battery is loaded with the three-dimensional grapheme of the flower-shaped nickel of curing three
Combination electrode, it is characterised in that in step 1), chemical vapor deposition concretely comprises the following steps：
Three-dimensional porous foams nickel is placed in reactor, 800~1200 DEG C, after insulation is warming up under an ar atmosphere, is re-introduced into first
Alkane, room temperature is cooled to after reaction.
3. the surface according to claim 1 applied to sodium-ion battery is loaded with the three-dimensional grapheme of the flower-shaped nickel of curing three
Combination electrode, it is characterised in that in step 3), described hydrothermal temperature is 110~130 DEG C.
4. the surface according to claim 1 applied to sodium-ion battery is loaded with the three-dimensional grapheme of the flower-shaped nickel of curing three
Combination electrode, it is characterised in that in described three-dimensional grapheme combination electrode the bearing capacity of the flower-shaped nickel of curing three be 0.8~
1.5mg/cm2, the bearing capacity of graphene is 0.3~0.6mg/cm2。
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| CN201610248533.0A CN105789592B (en) | 2016-04-20 | 2016-04-20 | Surface is loaded with three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three and its preparation method and application |
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| CN201610248533.0A CN105789592B (en) | 2016-04-20 | 2016-04-20 | Surface is loaded with three-dimensional grapheme combination electrode of the flower-shaped nickel of curing three and its preparation method and application |
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| CN106449172B (en) * | 2016-10-19 | 2018-07-24 | 安徽师范大学 | CdS@Ni3S2Nucleocapsid heterojunction structure composite material and preparation method and application |
| CN106784719B (en) * | 2017-01-05 | 2019-07-26 | 山东理工大学 | A kind of preparation method of the flower-shaped nickel sulfide/foam nickel material of graphene coated 3D |
| CN107086132B (en) * | 2017-04-26 | 2019-07-19 | 安徽师范大学 | Flower-shaped three nickel nano film of vanadic anhydride/curing and its preparation method and application |
| CN108123141A (en) * | 2017-12-07 | 2018-06-05 | 北京理工大学 | A kind of three-dimensional porous foams grapheme material and its application |
| CN109524245B (en) * | 2018-11-20 | 2020-09-18 | 东南大学 | Preparation method of high-performance nickel-cobalt selenide/three-dimensional graphene/foamed nickel binder-free electrode material |
| CN111233055B (en) * | 2020-01-14 | 2022-07-08 | 东南大学 | Preparation method of trinickel disulfide-three-dimensional graphene composite electrode material |
| CN112614992B (en) * | 2020-12-10 | 2022-08-16 | 三峡大学 | Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive electrode material |
| CN113511670B (en) * | 2021-07-26 | 2022-05-03 | 湖北工程学院 | Three-dimensional flower bunch-shaped structure nano material compounded with zinc sulfide on graphene oxide, application and preparation method |
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