CN110104630A - A kind of porous carbon composite and its preparation method and application for battery diaphragm - Google Patents
A kind of porous carbon composite and its preparation method and application for battery diaphragm Download PDFInfo
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- CN110104630A CN110104630A CN201910404607.9A CN201910404607A CN110104630A CN 110104630 A CN110104630 A CN 110104630A CN 201910404607 A CN201910404607 A CN 201910404607A CN 110104630 A CN110104630 A CN 110104630A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The purpose of the present invention is to provide porous carbon composites of a kind of battery diaphragm and its preparation method and application, belong to the technical field of electrochemistry new material.The preparation method of porous carbon composite of the invention, devise a kind of a kind of MOF composite material based on the adenine rich in N element, Ni is added in preparation process, and regulator of the cetyl trimethylammonium bromide (CTAB) as morphology and size is added, wherein under the catalysis of Ni, material internal grows a large amount of carbon nanotubes, form the structure of class sea urchin shape, based on this, each substance has been cross-linked to form mutually a three-dimensional conductive absorption conversion network in preparation process of the invention, a large amount of carbon nanotubes, which are generated, using Ni self-catalysis improves electric conductivity, also it avoids the need for that the conductive agents save the cost such as carbon nanotube is additionally added, utilize Ni3ZnC0.7The more lithium sulfide conversions of quick catalysis, the Ni and carbon nanotube of generation effectively facilitate the transfer of electronics, the cyclical stability and high rate performance of battery are greatly improved.
Description
Technical field
The invention belongs to the technical fields of the new material of electrochemistry, and in particular to a kind of porous carbon for battery diaphragm is multiple
Condensation material and its preparation method and application.
Background technique
The whole world produces the shortage of fossil fuel in the explosion demand for the high-efficiency and economic energy, petroleum, coal mine etc. one
Secondary fossil energy supply and demand situation in short supply is severeer, and bad environments trend allows of no optimist, and alternativeization is excavated in global urgent need
The green novel energy source of the stone energy.Electrochmical power source is the energy storage device that chemical electric energy and electric energy mutually convert, and becomes new energy project
One of research direction.Lithium ion battery is the novel green chemical energy source rapidly developed in recent decades.And lithium ion battery exists
It almost can achieve its theoretical specific capacity in the research of nearest decades, but be still unable to satisfy height ratio capacity and high specific energy
The demand of amount is finding next-generation high-energy density and economical and eco-friendly chargeable cell system, and lithium-sulfur cell is with its Gao Li
It is studied extensively by energy density (2600Wh/Kg) and high theoretical specific capacity (1675mAh/g) by people, the specific capacity of superelevation has no
Query has caused numerous researchs and concern.Not only lithium-sulfur cell has the theoretical energy density and specific volume of forenamed brilliance
Amount, and sulphur rich reserves and economy as positive electrode, before these advantages all allow lithium-sulfur cell to become at present most exploitation
One of secondary cell system of scape.Chargeable lithium-sulfur cell has attracted a large amount of scientific research close due to its superior energy
It spends and arouses attention.However, lithium-sulfur electrochemical reaction is related to polyelectron redox reaction, when process complexity phase transformation, most end form
The performance of battery, insulation and insoluble charge and discharge product are largely determined at the form sediment of solid-state lithium sulfide
(S and Li2S) lead to slow dynamics of oxidation reduction and low-sulfur utilization rate.Based on this, researcher designs and develops a variety of materials use
In solving the problems, such as lithium-sulfur cell.Such as design and exploitation, electrolyte as materials such as the positive electrode such as porous carbons for carrying sulphur
Optimization, the design of function diaphragm coating of formula etc..The modification of lithium-sulphur cell positive electrode takes under being continually striving to of researcher
Certain progress was obtained, the preferable anode pole piece of various chemical properties is had devised.However, between positive and negative anodes concentration gradient and
Under electric field action, dissolution diffusion still inevitably occurs for more sulphions, causes the loss of active material.Diaphragm is as lithium
The important component of sulphur battery, the important task that carry conducting ion, completely cut off electronics.The more lithium sulfides generated in reaction must be through
Crossing diaphragm could shuttle to cathode, it means that diagram modification is also a kind of effective means for inhibiting more lithium sulfides to shuttle.Wherein
The shuttle that one layer of diaphragm functional coating inhibits more sulphions is coated on diaphragm, since preparation process is simple, stable structure, coating
Lighter in weight, it is smaller to battery integral energy Effects of Density, it is a kind of more effective method.
It has been reported that lithium-sulfur cell diaphragm coating research in, carbon material can by its loose porous structure to anti-
More lithium sulfides of middle generation are answered to form physical absorption, to alleviate shuttle effect.The diagram modification of some doped metallic oxides
The study found that certain metal oxides have certain chemisorption to more lithium sulfides.This chemisorption can be more
Effectively inhibit the shuttle of more lithium sulfides, so that battery shows excellent cyclical stability and high rate performance.However due to gold
The electric conductivity for belonging to oxide is poor, and the more lithium sulfides adsorbed in the oxide are difficult to be fully utilized, so that the capacity of battery meets with
By partial loss.And carbon material, since it is weaker with the interaction of more lithium sulfides, the absorption to more lithium sulfides is usually object
Reason absorption, keeps the inhibitory effect of its effect that shuttles to it poor.In order to utilize the good electric conductivity of carbon material and gold simultaneously
Belong to the oxide chemisorption strong to more lithium sulfides, metal oxide and conductive carbon material are prepared into compound and applied
It will be a kind of good strategy comprehensively considered on function diaphragm coating.
In recent years, metal organic framework (MOFs) and using MOFs be the carbon material of presoma as novel sulfur-donor and function
Energy film coating materials have obtained extensive research in lithium battery.MOFs be by metal ion/cluster node for infinitely arranging and
The crystalline material of organic chain junctor composition, large specific surface area, size and aperture are adjustable, by the concern of people.It is with MOFs
The composite material of metallic compound and porous carbon can be simply prepared in presoma.
Summary of the invention
In view of the above problems, in order to solve to exist in the prior art the shuttle effect of the coating of battery diaphragm, electric conductivity compared with
The problems such as difference or chemical stability are poor, the invention proposes a kind of based on the compound rich in nitrogen, the porous carbon of nickel of MOF synthesis
Material and its preparation method and application.
The purpose of the present invention is to provide a kind of porous carbon composite materials for battery diaphragm, include for constituent
N, Ni and Ni3ZnC0.7Porous carbon composite, be rich in N, Ni and Ni3ZnC0.7。
The present invention also provides the preparation methods of the porous carbon composite for battery diaphragm, include the following steps:
1) zinc acetate, nickel acetate, cetyl trimethylammonium bromide (CTAB) mixed dissolution are taken, so that reaction raw materials are sufficiently molten
Solution, obtains solution A；
2) it takes adenine, 4,4- diphenyl dicarboxylic acid to dissolve respectively, is mixed after dissolution with solution A, so that organic ligand adenine
It is sufficiently dissolved with 4,4- diphenyl dicarboxylic acid, obtains solution B；
3) solution B, carbon nano-tube solution, methanol and deionized water is taken to be mixed, reaction raw materials and carbon nanotube are abundant
Mixing, reaction, reaction are centrifuged after terminating, and obtain grey powder；
4) by after the washing of grey powder, it is dried to obtain Ni-MOF compound, porous carbon composite wood is obtained after being calcined
Material, is named as Ni-MOF-800-8H；Unreacted impurity is removed by washing；By being carbonized under an inert atmosphere, obtain nickel,
The porous carbon materials of N doping；
Further, dissolution described in step 1) and step 2 includes n,N-Dimethylformamide (DMF) using solvent；
Carbon nano-tube solution in step 3) is to disperse activated solution in n,N-Dimethylformamide (DMF) in advance, will
Carbon nanotube in advance it is scattered so that nano particle it is more uniform growth on the carbon nanotubes；
Washing described in step 4) includes N,N-dimethylformamide (DMF) and methanol using solvent；
Calcining described in step 4) is high-temperature calcination under nitrogen atmosphere, and calcination condition is 800 DEG C of lasting 8h, utilizes height for a long time
The atmosphere of inert gases of temperature makes Ni self-catalysis generate carbon nanotube；It is catalyzed in an inert atmosphere using the elemental nickel that reduction obtains
Carbon material generates carbon nanotube, to improve material conductivity.
The present invention also provides the applications of the porous carbon composite for battery diaphragm, are applied to the painting of battery diaphragm
Layer material；
The preparation method of the coating material of the battery diaphragm includes the following steps: to take porous carbon composite of the present invention
Ni-MOF-800-8H made from preparation method, conductive agent, binder and the mixing of normal propyl alcohol solution are tuned into slurry, are coated
On battery diaphragm, it is dried, is sliced to get coated separator is arrived later；The carbon composite prepared is coated on diaphragm,
And assembled battery, to test coating material to the improvement situation of battery performance；
In the preparation method of the coating material of the battery diaphragm, conductive agent includes conductive black, and binder includes LA132；Charcoal
Black effect is to improve electric conductivity, and the effect of binder is to be adhered to material on diaphragm.
Beneficial effects of the present invention are as follows:
The preparation method of porous carbon composite of the invention devises a kind of a kind of MOF based on the adenine rich in N element
Composite material is added Ni in preparation process, and tune of the cetyl trimethylammonium bromide (CTAB) as morphology and size is added
Agent is saved, wherein material internal grows a large amount of carbon nanotubes under the catalysis of Ni, the structure of class sea urchin shape is formed, is based on this, this
Each substance has been cross-linked to form mutually a three-dimensional conductive absorption conversion network in the preparation process of invention, is produced using Ni self-catalysis
Raw a large amount of carbon nanotubes improve electric conductivity, also avoid the need for that the conductive agents save the cost such as carbon nanotube is additionally added, and utilize
Ni3ZnC0.7The more lithium sulfide conversions of quick catalysis, the Ni and carbon nanotube of generation effectively facilitate the transfer of electronics, electricity are greatly improved
The cyclical stability and high rate performance in pond；
Most of diaphragm coating is applied in lithium-sulfur cell at this stage, can not effectively quickly under high current density and high-sulfur carrying capacity
More lithium sulfide migrations are obstructed, causes battery discharge specific capacity to decay rapidly, can not also support under big sulphur carrying capacity and high current density
Stable long circulating, and porous carbon composite Ni-MOF-800-8H obtained by the present invention has excellent electrochemistry steady
Qualitative and higher coulombic efficiency effectively the more lithium sulfides of quick adsorption and can realize rapid catalytic conversion, effectively
Migration effect is inhibited, being applied in the diaphragm coating material of lithium-sulfur cell has great prospect.
Figure of description
Fig. 1 is the scanning electron microscope (SEM) photograph of Ni-MOF；
Fig. 2 is the scanning electron microscope (SEM) photograph of Ni-MOF-800-8H；
Fig. 3 is the coated separator sectional view of Ni-MOF-800-8H；
Fig. 4 is that the electrochemistry of the coated separator of Ni-MOF-800-8H recycles schematic diagram.
Specific embodiment
Below by way of specific case study on implementation and Detailed description of the invention, the present invention is described in further detail, it should be understood that this
A little embodiments are merely to illustrate the present invention rather than limit the scope of the invention, after the present invention has been read, ability
It is as defined in the appended claims that field technique personnel fall within the application to the modification of various equivalent forms of the invention.
If all raw materials and reagents of the invention are the raw material of conventional market, reagent without specified otherwise.
Embodiment 1
A kind of preparation method of the porous carbon composite for battery diaphragm:
1) zinc acetate, nickel acetate, cetyl trimethylammonium bromide is taken to be dissolved in ultrasonic dissolution in DMF with the molar ratio of 9:1:1,
Obtain solution A；
2) adenine is taken, 4,4- diphenyl dicarboxylic acids are dissolved in ultrasonic dissolution in same volume DMF with the molar ratio of 1:1 respectively, obtain
The solution arrived is mixed with solution A, obtains solution B；
3) solution B is taken, the activated carbon nano-tube solution being dispersed in DMF, methanol and the deionization that volume ratio is 5:4:1
Water is mixed, and reaction is centrifuged after terminating, and obtains grey powder；
4) after successively washing grey powder with DMF, MeOH, Ni-MOF is obtained after drying in an oven, by MOF in nitrogen atmosphere
Under tube furnace in calcine, calcination condition is 800 degree of 8h, heating rate is 5 DEG C/min, and calcined product is named as Ni-MOF-
800-8H；
Ni-MOF-800-8H, Super-P, LA132 binder made from Example 1 utilize positive third according to the ratio of 6:2:2
Alcoholic solution is dispersed to be tuned into slurry, is coated onto PP(Celgard-2400) on diaphragm, in 60 DEG C of vacuum oven
It is dry for 24 hours, be cut into disk size that diameter is 19mm using slicer to get the coated separator for arriving Ni-MOF-800-8H.
Embodiment 2
A kind of preparation method of the porous carbon composite for battery diaphragm:
1) zinc acetate, nickel acetate, cetyl trimethylammonium bromide is taken to be dissolved in ultrasonic dissolution in DMF with the molar ratio of 8:1:1,
Obtain solution A；
2) adenine is taken, 4,4- diphenyl dicarboxylic acids are dissolved in ultrasonic dissolution in same volume DMF with the molar ratio of 1:1 respectively, obtain
The solution arrived is mixed with solution A, obtains solution B；
3) solution B is taken, the activated carbon nano-tube solution being dispersed in DMF, methanol and the deionization that volume ratio is 5:4:1
Water is mixed, and reaction is centrifuged after terminating, and obtains grey powder；
4) after successively washing grey powder with DMF, MeOH, Ni-MOF is obtained after drying in an oven, by MOF in nitrogen atmosphere
Under tube furnace in calcine, calcination condition is 800 degree of 8h, heating rate is 5 DEG C/min, and calcined product is named as Ni-MOF-
800-8H；
Ni-MOF-800-8H, Super-P, LA132 binder made from Example 1 utilize positive third according to the ratio of 6:2:2
Alcoholic solution is dispersed to be tuned into slurry, is coated onto PP(Celgard-2400) on diaphragm, in 60 DEG C of vacuum oven
It is dry for 24 hours, be cut into disk size that diameter is 19mm using slicer to get the coated separator for arriving Ni-MOF-800-8H.
Embodiment 3
A kind of preparation method of the porous carbon composite for battery diaphragm:
1) zinc acetate, nickel acetate, cetyl trimethylammonium bromide is taken to be dissolved in ultrasonic dissolution in DMF with the molar ratio of 7:1:1,
Obtain solution A；
2) adenine is taken, 4,4- diphenyl dicarboxylic acids are dissolved in ultrasonic dissolution in same volume DMF with the molar ratio of 1:1 respectively, obtain
The solution arrived is mixed with solution A, obtains solution B；
3) solution B is taken, the activated carbon nano-tube solution being dispersed in DMF, methanol and the deionization that volume ratio is 5:4:1
Water is mixed, and reaction is centrifuged after terminating, and obtains grey powder；
4) after successively washing grey powder with DMF, MeOH, Ni-MOF is obtained after drying in an oven, by MOF in nitrogen atmosphere
Under tube furnace in calcine, calcination condition is 800 degree of 8h, heating rate is 5 DEG C/min, and calcined product is named as Ni-MOF-
800-8H；
Ni-MOF-800-8H, Super-P, LA132 binder made from Example 3 utilize positive third according to the ratio of 6:2:2
Alcoholic solution is dispersed to be tuned into slurry, is coated onto PP(Celgard-2400) on diaphragm, in 60 DEG C of vacuum oven
It is dry for 24 hours, be cut into disk size that diameter is 19mm using slicer to get the coated separator for arriving Ni-MOF-800-8H.
The scanning electron microscope (SEM) photograph of obtained Ni-MOF is as shown in Figure 1, obtained Ni-MOF- in the embodiment of the present invention
The scanning electron microscope (SEM) photograph of 800-8H is as shown in Fig. 2, form a three-dimensional conductive absorption conversion network structure；Obtained Ni-
The section of the coated separator of MOF-800-8H is as shown in figure 3, only have 4 μm or so of thickness.
Comparative experiments: by S(sulfur material) and Ketjen black (conductive black) it is anti-in 155 DEG C of reaction kettles according to the ratio of 1:4
It answers 24 hours and is prepared into C/S compound, by C/S compound, Super-P, LA132 binder according to the ratio of 8:1:1 using just
Propanol solution dispersion is prepared into slurry, is coated on aluminium foil, dries for 24 hours in 60 DEG C of vacuum oven.Utilize slice
Machine is cut into the electrode disk that diameter is 12mm, and being prepared into sulphur carrying capacity respectively using the scraper of different-thickness is 2 mg/cm2、6
mg/cm2Pole piece.In glove box, with prepared pole piece be anode, lithium piece is to cathode, PP(Celgard-2400) every
Film or the PP(Celgard-2400 for being coated with material) diaphragm, 1.0 M LiTFSI DOL/DME (v:v, 1:1) be electrolysis
Liquid is assembled into CR-2302 button cell, and wherein coat is towards C/S anode.
With the chemical property of battery test system test battery, as shown in figure 4, coated separator material of the invention exists
In 2 mg/cm2Face carry and can recycle 1200 circles under sulfur content with the excess current densities of 5C and still maintain the electric discharge of 400 mAh/g
Specific capacity, it can be seen that discharge performance is stablized, and having recycled 1200 circles still maintains comparable specific discharge capacity, and coulombic efficiency is steady
It is scheduled on 100% or so, does not occur the phenomenon that overcharges, it was demonstrated that Ni-MOF-800-8H material produced by the present invention can be effectively fast
Speed adsorbs more lithium sulfides and realizes rapid catalytic conversion, restrained effectively migration effect, in the diaphragm coating of lithium-sulfur cell
It is upper that there is great prospect.
Claims (8)
1. a kind of porous carbon composite for battery diaphragm, which is characterized in that its for constituent include N, Ni and
Ni3ZnC0.7Porous carbon composite.
2. a kind of preparation method of the porous carbon composite for battery diaphragm, which comprises the steps of:
1) zinc acetate, nickel acetate, cetyl trimethylammonium bromide mixed dissolution are taken, solution A is obtained；
2) it takes adenine, 4,4- diphenyl dicarboxylic acid to dissolve respectively, is mixed after dissolution with solution A, obtain solution B；
3) solution B, carbon nano-tube solution, methanol and deionized water is taken to be mixed, reaction is centrifuged after terminating, and is obtained
Grey powder；
4) by after the washing of grey powder, it is dried to obtain Ni-MOF compound, porous carbon composite wood is obtained after being calcined
Material, is named as Ni-MOF-800-8H.
3. by the preparation method of the porous carbon composite as claimed in claim 2 for battery diaphragm, which is characterized in that step
1) and the solvent that uses of dissolution described in step 2 includes N,N-dimethylformamide.
4. by the preparation method of the porous carbon composite described in claim 2 or 3 for battery diaphragm, which is characterized in that
Carbon nano-tube solution in step 3) is to disperse activated solution in N,N-dimethylformamide in advance.
5. by the preparation method of the porous carbon composite as claimed in claim 4 for battery diaphragm, which is characterized in that step
4) washing described in includes N,N-dimethylformamide and methanol using solvent.
6. a kind of application of the porous carbon composite for battery diaphragm, which is characterized in that its painting for being applied to battery diaphragm
Layer material.
7. by the application of the porous carbon composite as claimed in claim 6 for battery diaphragm, which is characterized in that the battery
The preparation method of the coating material of diaphragm includes the following steps: to take Ni-MOF-800- made from preparation method described in claim 2
8H, conductive agent, binder and the mixing of normal propyl alcohol solution are tuned into slurry, are coated on battery diaphragm, be dried later,
It is sliced to get coated separator is arrived.
8. the application as described in claim 6 or 7 for the porous carbon composite of battery diaphragm, which is characterized in that described
In the preparation method of the coating material of battery diaphragm, conductive agent includes conductive black, and binder includes LA132.
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Cited By (12)
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| CN111001428A (en) * | 2019-12-24 | 2020-04-14 | 山西大学 | Metal-free carbon-based electrocatalyst, preparation method and application |
| CN113851785A (en) * | 2021-10-22 | 2021-12-28 | 陕西科技大学 | FeNi alloy composite CNTs modified diaphragm and preparation method and application thereof |
| CN113964447A (en) * | 2021-10-22 | 2022-01-21 | 陕西科技大学 | Battery diaphragm modified by sulfur-doped iron-nickel alloy/carbon nanotube composite material and preparation method thereof |
| CN113964446A (en) * | 2021-10-22 | 2022-01-21 | 陕西科技大学 | Fe. Co-codoped CuZnInNi/CNTs modified battery diaphragm, preparation method thereof and lithium fluorocarbon battery |
| CN113972437A (en) * | 2021-10-22 | 2022-01-25 | 陕西科技大学 | Battery diaphragm modified by zinc-nickel alloy/carbon nanotube composite material and preparation method thereof |
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| CN113991242A (en) * | 2021-10-22 | 2022-01-28 | 陕西科技大学 | InNi/CNTs modified battery diaphragm, preparation method thereof and lithium fluorocarbon battery |
| CN114956039A (en) * | 2022-06-09 | 2022-08-30 | 西安理工大学 | Hollow sea urchin-shaped double-metal MOFs (metal-organic frameworks) derived carbon material as well as preparation method and application thereof |
| CN114976484A (en) * | 2022-07-11 | 2022-08-30 | 大连理工大学 | Loaded with Ni 2 P-Co Schottky junction active site urchin-shaped carbon material electrocatalyst, preparation method and application thereof |
| CN115513468A (en) * | 2022-11-22 | 2022-12-23 | 河北北方学院 | Preparation method of CNTs/OMC ordered microporous carbon nanospheres and application method of CNTs/OMC ordered microporous carbon nanospheres in lithium-sulfur battery |
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