CN105789592A - Three-dimensional graphene composite electrode with surface carrying flowerlike Ni3S2 and preparation method and application thereof - Google Patents
Three-dimensional graphene composite electrode with surface carrying flowerlike Ni3S2 and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional graphene composite electrode with three-dimensional porous foamed nickel as a base body. Graphene directly grows on the base body, and flowerlike Ni3S2 directly grows on the graphene. The invention further discloses a preparation method and application of the three-dimensional graphene composite electrode. The preparation method has the advantages of being simple in process, low in cost, short in period, low in energy consumption and the like and is suitable for large-scale industrial production. The prepared three-dimensional graphene composite electrode does not contain any conductive agent and adhesive. Due to the special three-dimensional porous structure and the conductive and fixing function of the flowerlike Ni3S2 and graphene, when used for a sodium-ion battery, the composite electrode shows high capacity and good circulation stability.
Description
Technical field
The present invention relates to sodium-ion battery combination electrode field, be specifically related 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 now, such as smart mobile phone, notebook computer etc., and has huge market in electrical network energy storage, electric automobile field.But, along with popularizing of lithium ion battery, particularly large-scale use on electric automobile, the consumption of lithium resource is also huge.And the reserves of lithium resource are limited, and at present the recovery of elemental lithium in waste lithium ion is lacked effective, economic technology.By contrast, sodium element reserves on earth are significantly larger than elemental lithium, and price is also far below lithium.Therefore, in recent years, sodium-ion battery is subject to extensive attention.It is generally believed that sodium-ion battery has tempting prospect in electrical network energy storage field.
Traditional lithium ion battery uses graphite as negative pole, but owing to the radius of sodium ion is much larger than lithium ion, sodium ion is difficult to be embedded between graphite linings.Therefore, the storage sodium capacity of graphite, far below lithium storage content, is generally below 300mAh/g.In consideration of it, development of new high power capacity storage sodium negative material has become the key factor that sodium-ion battery is researched and developed.Embedding the graphite type material of mechanism relative to sodium ion, can there is reversible conversion reaction in some sulfide and sodium, the storage sodium capacity that this storage sodium mechanism is corresponding higher.As following reaction can occur NiS and Na:The theory storage sodium capacity of this reaction is up to 590mAh/g.
Although sulfide has higher storage sodium activity, but owing to sulfide electrical conductivity is relatively low, affect the performance of its storage sodium activity, it is necessary to add conductive carbon and improve the conductivity of electrode.It addition, for traditional coating processes, generally require polymeric binder and active particle fixed.
By being directly grown on conducting base by active material, can improving electrical conductivity on the one hand, the opposing party can avoid using polymeric binder.Graphene, because its high electrical conductivity, high mechanical strength, big specific surface area agent, is ideal matrix material.Use Graphene can meet conduction and fixation as matrix simultaneously, sodium-ion battery electrode design has good prospect, but there is presently no the bibliographical information of this respect.
Summary 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 combination electrode prepared has high power capacity and high cyclical stability, is applied in sodium-ion battery electrode, can be used to improve the chemical property of sodium-ion battery, particularly improves capacity and cyclical stability.
The invention discloses the preparation method that a kind of surface is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, comprise the following steps:
1) with three-dimensional porous foams nickel for matrix, by chemical vapour deposition technique, on matrix, directly grow Graphene, be designated as Ni/G；
2) thiourea and anhydrous sodium sulfate are dissolved in deionized water, are uniformly mixing to obtain mixed solution, SO in described mixed solution4 2–Concentration is 0.01～0.05mol/L；
The mol ratio of described thiourea and anhydrous sodium sulfate is 0.2～1.0；
3) by step 1) Ni/G that obtains immerses step 2) mixed solution that obtains, through 100～150 DEG C of hydro-thermal reaction 1～5h, it is loaded with, then through washing, dried surface of must arriving, the Ni/G being loaded with curing three nickel, is designated as Ni/G/Ni3S2。
The present invention, with three-dimensional porous foams nickel for matrix, directly prepares Graphene by CVD on matrix, and described Graphene replicates the three-dimensional porous structure of nickel foam；Again through hydro-thermal method at three-dimensional grapheme surface direct growth flower-shape Ni3S2.Graphene serves dual function, is not only Ni3S2Electric action is provided, and flower-shape Ni can be fixed3S2, thus improving its capacity and cyclical stability.
Described direct growth refers to: first pass through CVD, directly prepares Graphene on the skeleton of nickel foam；Then under hydrothermal conditions, flower-shape Ni3S2It is directly grown on Graphene；In contrast, non-immediate growth refers to pre-synthesis Graphene and flower-shape Ni3S2, then by two kinds of raw materials and binding agent mix homogeneously in organic solvent, stir into slurry, then repaste and be distributed on nickel foam substrate.
As preferably, step 1) in, concretely comprising the following steps of chemical vapour deposition (CVD):
Three-dimensional porous foams nickel is placed in reactor, is warming up to 800～1200 DEG C under an ar atmosphere, after insulation, be re-introduced into methane, after reaction, be cooled to room temperature.
As preferably, putting in tube furnace by three-dimensional porous foams nickel, it is warming up to 1000 DEG C under an ar atmosphere, after insulation, then with Ar air-flow, methane is introduced in quartz ampoule, react 3～10min；Finally, it is cooled to room temperature under an ar atmosphere, obtains the three-dimensional grapheme being grown on nickel foam substrate；It is designated as Ni/G.
As preferably, step 3) in, described hydrothermal temperature is 110～130 DEG C.
The temperature of described cooling does not have strict restriction, based on adequate operation, generally can be cooled to the ambient temperature of 15～30 DEG C.
The invention also discloses the surface prepared according to above-mentioned method and be loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, described three-dimensional grapheme combination electrode material is with three-dimensional porous foams nickel for matrix, direct growth Graphene on matrix, on described Graphene, direct growth flower-shaped curing three nickel, is designated as Ni/G/Ni3S2。
Ni in the present invention3S2Coming from metallic nickel, therefore flower-shaped curing three nickel is inevitable is connected with metallic nickel matrix.Further, since at Ni3S2Graphene, Ni is grown in advance before growth3S2Nanometer sheet necessarily runs through graphene sheet layer, therefore flower-shape Ni3S2Graphene sheet layer can be run through and by UNICOM of graphene sheet layer institute.Therefore, this combination electrode has necessarily had performance and mechanical performance.
Flower-shape Ni3S2There is less size and higher specific surface area, be conducive to the raising by electrolyte moistening and material activity.As preferably, described flower-shape Ni3S2By circular Ni3S2Thin slice forms, monolithic Ni3S2Diameter be 2～3 μm, monolithic Ni3S2Thickness be only 100～200nm.Relatively thin monolithic Ni3S2Be conducive to the diffusion of sodium ion, thus improving the activity of material.
As preferably, in described three-dimensional grapheme combination electrode material, the bearing capacity of flower-shaped curing three nickel is 0.8～1.5mg/cm2.Flower-shape Ni3S2Bearing capacity very few, the capacity of electrode is just relatively low；Bearing capacity is too much, material not easily by electrolyte moistening, Graphene to conduction and fixation can weaken.
As preferably, the bearing capacity of Graphene is 0.3～0.6mg/cm2, Graphene plays conduction and fixation, the mechanical stability of the too low raising being unfavorable for electric conductivity of Graphene content and electrode in the electrodes, and too high content is inconspicuous to the effect of electric conductivity and the raising of mechanical performance.Therefore, the content of Graphene is controlled in above-mentioned scope more reasonable.
The invention also discloses this surface and be loaded with the application in sodium-ion battery of the three-dimensional grapheme combination electrode of flower-shaped curing three nickel.
Compared with prior art, present invention have the advantage that
1, Graphene and flower-shape Ni in the three-dimensional grapheme combination electrode that prepared by the present invention3S2It is directly grown on nickel foam substrate, without other conductive agents and binding agent, has that technique is simple, cost is low, the cycle is short, energy consumption is low and the advantage such as applicable industrialized production；
2, in the three-dimensional grapheme combination electrode that prepared by the present invention, Graphene simultaneously works as conduction and fixation, can improve electro-chemical activity and the mechanical stability of electrode, thus improving capacity and the cyclical stability of electrode；
3, compared with traditional electrode slurry coating process, this preparation method can keep the original three-dimensional porous structure of nickel foam, is conducive to the moistening of electrode and the buffering of stress, thus improving the cyclical stability of sodium-ion battery.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the three-dimensional grapheme combination electrode surface mass of embodiment 1 preparation；
Fig. 2 is Raman (Raman) spectrogram of the Ni/G of embodiment 1 preparation；
Fig. 3 is the low power stereoscan photograph of the three-dimensional grapheme combination electrode of embodiment 1 preparation；
Fig. 4 is the high power stereoscan photograph of the three-dimensional grapheme combination electrode of embodiment 1 preparation；
Fig. 5 be respectively three-dimensional grapheme combination electrode with embodiment 1 preparation is positive pole, the cyclical stability (a) of sodium-ion battery that assembles for negative pole of metallic sodium, and the electrode prepared with comparative example 1 be positive pole, the cyclical stability (b) of sodium-ion battery that assembles for negative pole of metallic sodium.
Detailed description of the invention
Embodiment 1
Nickel foam is put in tube furnace, under Ar (500s.c.c.m.) atmosphere, be warming up to 1000 DEG C with the programming rate of 100 DEG C/min；After being incubated 5 minutes, with Ar (250s.c.c.m.) air-flow, methane is introduced in quartz ampoule, react 5 minutes；Finally, it is cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtains the three-dimensional grapheme (Ni/G) being grown on nickel foam substrate, wherein the bearing capacity 0.485mg/cm of Graphene2；Thiourea 0.4 times of anhydrous sodium sulfate (mole be) and anhydrous sodium sulfate being dissolved in deionized water, stirs, preparation is with SO4 2–Meter concentration is the solution of 0.03mol/L；Using Ni/G as matrix, immerse above-mentioned solution, retransfer in reactor, after airtight, in the baking oven of 120 DEG C, be incubated 3 hours, then rinse for several times with deionized water and anhydrous alcohol, the Ni being carried on Ni/G must be loaded with at the baking oven vacuum dryings of 60 DEG C to surface after 12 hours3S2 (Ni/G/Ni3S2), wherein Ni3S2Bearing capacity be 1.03mg/cm2。
Fig. 1 is the Ni/G/Ni of this enforcement preparation3S2The X-ray diffraction spectrum of electrode, this material can be attributed to Ni3S2And Graphene.
Fig. 2 is the Raman spectrum of the Ni/G of preparation, and stronger 2D peak shows that Graphene is minority Rotating fields.
The G/Ni being carried in nickel foam prepared by Fig. 3 and Fig. 4 respectively the present embodiment3S2The low power of electrode and high power scanning electron microscope, from photo it can be seen that Ni3S2Present flower-like structure, flower-shape Ni3S2By circular Ni3S2Thin slice forms, and monolithic wafer diameters is 2 microns～3 microns, and thickness is 100～200nm, and uniform load is on three-dimensional grapheme.
With the G/Ni being carried in nickel foam prepared by the present embodiment3S2As positive pole, with metallic sodium for negative pole, glass fibre (trade mark WhatmanGF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, assemble in the glove box of full argon, carry out charge-discharge test, in cycle life curve such as Fig. 5 shown in curve (a).
Constant current charge-discharge test (electric current density 50mA/g, voltage range 0.005V～3V, wherein capacity and electric current density are based on the weight of curing three nickel) show, circulation volume is 453mAh/g first, circulating through 60 times, capacity is maintained at 267mAh/g.
Comparative example 1
Ni3S2Preparation technology and embodiment 1 identical, difference is Ni3S2It is directly grown on Ni substrate, Ni substrate does not grow Graphene in advance.Concrete technology is as follows, thiourea 0.4 times of anhydrous sodium sulfate (mole be) and anhydrous sodium sulfate is dissolved in deionized water, stirs, and preparation is with SO4 2–Meter concentration is the solution of 0.03mol/L；Using foam nickel sheet (without Graphene) as matrix, immerse above-mentioned solution, retransfer in reactor, in the baking oven of 120 DEG C, it is incubated 3 hours after airtight, then rinse for several times with deionized water and anhydrous alcohol, the Ni being carried on Ni must be loaded with at the baking oven vacuum dryings of 60 DEG C to surface after 12 hours3S2(Ni/Ni3S2), wherein Ni3S2Bearing capacity be 1.02mg/cm2.X-ray diffraction spectrum shows, gained material is Ni3S2.Stereoscan photograph shows, Ni3S2Present flower-like structure, flower-shape Ni3S2By circular Ni3S2Thin slice forms, and monolithic wafer diameters is 2 microns～3 microns, and thickness is 200～300nm, and uniform load is on three-dimensional grapheme.
With the Ni being carried in nickel foam prepared by the present embodiment3S2As positive pole, with metallic sodium for negative pole, glass fibre (trade mark WhatmanGF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, assemble in the glove box of full argon, carry out charge-discharge test, see curve (b) in Fig. 5.
Constant current charge-discharge test (electric current density 50mA/g, voltage range 0.005V～3V, wherein capacity and electric current density are based on the weight of curing three nickel) shows, circulation volume is 368mAh/g first, circulates through 60 times, and capacity reduces to 164mAh/g.
Embodiment 2
Nickel foam is put in tube furnace, under Ar (500s.c.c.m.) atmosphere, be warming up to 1000 DEG C with the programming rate of 100 DEG C/min；After being incubated 5 minutes, with Ar (250s.c.c.m.) air-flow, methane is introduced in quartz ampoule, react 8 minutes；Finally, it is cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtains the three-dimensional grapheme (Ni/G) being grown on nickel foam substrate, wherein the bearing capacity 0.51mg/cm of Graphene2；Thiourea (the 0.2 of mole anhydrous sodium sulfate) and anhydrous sodium sulfate being dissolved in deionized water, stirs, preparation is with SO4 2–Meter concentration is the solution of 0.05mol/L；Using Ni/G as matrix, immerse above-mentioned solution, retransfer in reactor, after airtight, in the baking oven of 110 DEG C, be incubated 4 hours, then rinse for several times with deionized water and anhydrous alcohol, the Ni being carried on Ni/G must be loaded with at the baking oven vacuum dryings of 60 DEG C to surface after 12 hours3S2(Ni/G/Ni3S2), wherein Ni3S2Bearing capacity be 0.93mg/cm2.X-ray diffraction spectrum shows, gained material is Ni3S2And Graphene.The Raman spectrum of Ni/G shows, Graphene is minority Rotating fields.Stereoscan photograph shows, Ni3S2Present flower-like structure, flower-shape Ni3S2By circular Ni3S2Thin slice forms, and the diameter of monolithic thin slice is 2 microns～3 microns, and thickness is 100～200nm, and uniform load is on three-dimensional grapheme.
With the G/Ni being carried in nickel foam prepared by the present embodiment3S2As positive pole, with metallic sodium for negative pole, glass fibre (trade mark WhatmanGF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, assemble in the glove box of full argon, carry out charge-discharge test.
Constant current charge-discharge test (electric current density 50mA/g, voltage range 0.005V～3V, wherein capacity and electric current density are based on the weight of curing three nickel) show, circulation volume is 461mAh/g first, circulating through 60 times, capacity is maintained at 272mAh/g.
Embodiment 3
Nickel foam is put in tube furnace, under Ar (500s.c.c.m.) atmosphere, be warming up to 1000 DEG C with the programming rate of 100 DEG C/min；After being incubated 5 minutes, with Ar (250s.c.c.m.) air-flow, ethanol is introduced in quartz ampoule, react 3 minutes；Finally, it is cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtains the three-dimensional grapheme (Ni/G) being grown on nickel foam substrate, wherein the bearing capacity 0.32mg/cm of Graphene2；Thiourea (the 0.6 of mole anhydrous sodium sulfate) and anhydrous sodium sulfate being dissolved in deionized water, stirs, preparation is with SO4 2–Meter concentration is the solution of 0.02mol/L；Using Ni/G as matrix, immerse above-mentioned solution, retransfer in reactor, after airtight, in the baking oven of 130 DEG C, be incubated 2 hours, then rinse for several times with deionized water and anhydrous alcohol, the Ni being carried on Ni/G must be loaded with at the baking oven vacuum dryings of 60 DEG C to surface after 12 hours3S2(Ni/G/Ni3S2), wherein Ni3S2Bearing capacity be 1.01mg/cm2.X-ray diffraction spectrum shows, gained material is Ni3S2And Graphene.The Raman spectrum of Ni/G shows, Graphene is minority Rotating fields.Stereoscan photograph shows, Ni3S2Present flower-like structure, flower-shape Ni3S2By circular Ni3S2Thin slice forms, and the diameter of monolithic thin slice is 2 microns～3 microns, and thickness is 100～200nm, and uniform load is on three-dimensional grapheme.
With the G/Ni being carried in nickel foam prepared by the present embodiment3S2As positive pole, with metallic sodium for negative pole, glass fibre (trade mark WhatmanGF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, assemble in the glove box of full argon, carry out charge-discharge test.
Constant current charge-discharge test (electric current density 50mA/g, voltage range 0.005V～3V, wherein capacity and electric current density are based on the weight of curing three nickel) show, circulation volume 445 is mAh/g first, circulating through 60 times, capacity is maintained at 254mAh/g.
Embodiment 4
Nickel foam is put in tube furnace, under Ar (500s.c.c.m.) atmosphere, be warming up to 1000 DEG C with the programming rate of 100 DEG C/min；After being incubated 5 minutes, with Ar (250s.c.c.m.) air-flow, ethanol is introduced in quartz ampoule, react 10 minutes；Finally, it is cooled to room temperature with the cooling rate of 100 DEG C/min under an ar atmosphere, obtains the three-dimensional grapheme (Ni/G) being grown on nickel foam substrate, wherein the bearing capacity 0.55mg/cm of Graphene2；Thiourea (the 0.8 of mole anhydrous sodium sulfate) and anhydrous sodium sulfate being dissolved in deionized water, stirs, preparation is with SO4 2–Meter concentration is the solution of 0.02mol/L；Using Ni/G as matrix, immerse above-mentioned solution, retransfer in reactor, after airtight, in the baking oven of 120 DEG C, be incubated 4 hours, then rinse for several times with deionized water and anhydrous alcohol, the Ni being carried on Ni/G must be loaded with at the baking oven vacuum dryings of 60 DEG C to surface after 12 hours3S2(Ni/G/Ni3S2), wherein Ni3S2Bearing capacity be 1.13mg/cm2.X-ray diffraction spectrum shows, gained material is Ni3S2And Graphene.The Raman spectrum of Ni/G shows, Graphene is minority Rotating fields.Stereoscan photograph shows, Ni3S2Present flower-like structure, flower-shape Ni3S2By circular Ni3S2Thin slice forms, and the diameter of monolithic thin slice is 2 microns～3 microns, and thickness is 100～200nm, and uniform load is on three-dimensional grapheme.
With the G/Ni being carried in nickel foam prepared by the present embodiment3S2As positive pole, with metallic sodium for negative pole, glass fibre (trade mark WhatmanGF/D) is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, assemble in the glove box of full argon, carry out charge-discharge test.
Constant current charge-discharge test (electric current density 50mA/g, voltage range 0.005V～3V, wherein capacity and electric current density are based on the weight of curing three nickel) show, circulation volume is 464mAh/g first, circulating through 60 times, capacity is maintained at 277mAh/g.
Claims (8)
1. the preparation method that a surface is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, it is characterised in that comprise the following steps:
1) with three-dimensional porous foams nickel for matrix, by chemical vapour deposition technique, on matrix, directly grow Graphene, be designated as Ni/G；
2) thiourea and anhydrous sodium sulfate are dissolved in deionized water, are uniformly mixing to obtain mixed solution, SO in described mixed solution4 2–Concentration is 0.01～0.05mol/L；
The mol ratio of described thiourea and anhydrous sodium sulfate is 0.2～1.0；
3) by step 1) Ni/G that obtains immerses step 2) mixed solution that obtains, through 100～150 DEG C of hydro-thermal reaction 1～5h, it is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel then through washing, dried surface of must arriving, is designated as Ni/G/Ni3S2。
2. the preparation method that surface according to claim 1 is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, it is characterised in that step 1) in, concretely comprising the following steps of chemical vapour deposition (CVD):
Three-dimensional porous foams nickel is placed in reactor, is warming up to 800～1200 DEG C under an ar atmosphere, after insulation, be re-introduced into methane, after reaction, be cooled to room temperature.
3. the preparation method that surface according to claim 1 is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, it is characterised in that step 3) in, described hydrothermal temperature is 110～130 DEG C.
4. the surface that prepared by a method according to claim 1 is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, it is characterized in that, described three-dimensional grapheme combination electrode is with three-dimensional porous foams nickel for matrix, direct growth Graphene on matrix, direct growth flower-shaped curing three nickel on described Graphene.
5. surface according to claim 4 is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, it is characterized in that, described flower-shaped curing three nickel is connected with metallic nickel matrix, and flower-shaped curing three nickel runs through graphene sheet layer and by UNICOM of graphene sheet layer institute.
6. surface according to claim 5 is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, it is characterised in that described flower-shaped curing three nickel is by circular Ni3S2Thin slice forms, and the diameter of monolithic thin slice is 2～3 μm, and thickness is 100～200nm.
7. surface according to claim 6 is loaded with the three-dimensional grapheme combination electrode of flower-shaped curing three nickel, it is characterised in that in described three-dimensional grapheme combination electrode, the bearing capacity of flower-shaped curing three nickel is 0.8～1.5mg/cm2, the bearing capacity of Graphene is 0.3～0.6mg/cm2。
8. the surface according to claim 4～7 any claim is loaded with the application in sodium-ion battery of the three-dimensional grapheme combination electrode of flower-shaped curing three nickel.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107086132A (en) * | 2017-04-26 | 2017-08-22 | 安徽师范大学 | Flower-shaped nickel nano film of vanadic anhydride/curing three 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 |
| CN109524245A (en) * | 2018-11-20 | 2019-03-26 | 东南大学 | A kind of preparation method of high-performance nickel-cobalt selenides/three-dimensional grapheme/nickel foam binder free electrode material |
| CN111233055A (en) * | 2020-01-14 | 2020-06-05 | 东南大学 | Preparation method of trinickel disulfide-three-dimensional graphene composite electrode material |
| CN112614992A (en) * | 2020-12-10 | 2021-04-06 | 三峡大学 | Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive electrode material |
| CN113511670A (en) * | 2021-07-26 | 2021-10-19 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106449172A (en) * | 2016-10-19 | 2017-02-22 | 安徽师范大学 | CdS @ Ni3S2 core-shell heterostructure composite material, preparation method and application thereof |
| 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 |
| CN106784719A (en) * | 2017-01-05 | 2017-05-31 | 山东理工大学 | A kind of preparation method of the flower-shaped nickel sulfide/foam nickel materials of graphene coated 3D |
| 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 |
| CN107086132A (en) * | 2017-04-26 | 2017-08-22 | 安徽师范大学 | Flower-shaped nickel nano film of vanadic anhydride/curing three 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 |
| CN109524245A (en) * | 2018-11-20 | 2019-03-26 | 东南大学 | A kind of preparation method of high-performance nickel-cobalt selenides/three-dimensional grapheme/nickel foam binder free electrode material |
| 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 |
| CN111233055A (en) * | 2020-01-14 | 2020-06-05 | 东南大学 | Preparation method of trinickel disulfide-three-dimensional graphene composite 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 |
| CN112614992A (en) * | 2020-12-10 | 2021-04-06 | 三峡大学 | Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive 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 |
| CN113511670A (en) * | 2021-07-26 | 2021-10-19 | 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 |
| 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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