CN103762347A - Electrode material and preparation method thereof - Google Patents
Electrode material and preparation method thereof Download PDFInfo
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- CN103762347A CN103762347A CN201410033929.4A CN201410033929A CN103762347A CN 103762347 A CN103762347 A CN 103762347A CN 201410033929 A CN201410033929 A CN 201410033929A CN 103762347 A CN103762347 A CN 103762347A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 invention provides an electrode material and a preparation method thereof. The electrode material is characterized by comprising a porous carbon matrix and nanocrystalline metal polysulfide, wherein the nanocrystalline metal polysulfide is filled in pores of the porous carbon matrix; the sulfur content of the electrode material is more than 50 percent. The preparation method is characterized by comprising the following steps: 1, dissolving a metal salt in water, loading the prepared metal salt solution into the porous carbon matrix through a penetration technology, and drying the carbon matrix; 2, performing a reduction reaction on the carbon matrix loaded with the metal salt in the step 1, and preparing a carbon matrix loaded with nano metal particles; and 3, dripping the prepared sulfur-containing carbon disulfide solution into the carbon matrix loaded with nanocrystalline metals, reacting, removing the solvent through a drying process, and preparing the electrode material. According to the electrode material, the cycle performance of the electrode material can be improved, the high-rate performance is also improved, and the electrode material has high practicality.
Description
Technical field
The present invention relates to a kind of electrode material and preparation method thereof.
Background technology
Along with social development, environmental protection problem is more and more paid attention to by people.Environmental problems such as acid rain, greenhouse effect, urban heat land effect or display Ni Duan for the first time, or the mankind are caused to huge harm, being created in to a great extent of these environmental problems used fossil energy relevant with the mankind in a large number.Meanwhile, due to the swift and violent increase of energy-output ratio, fossil energy can not meet the demand of rapid economic development, and the target of paying close attention to is shifted to the development and utilization of new forms of energy in countries in the world.Development new forms of energy and regeneration clean energy technology are in 21 century development of world economy, to have material technology most.Wherein, the chemical energy storage devices such as the energy-storage battery that the lithium ion battery of take is representative and ultracapacitor are because it is most important in the grand strategy fields such as advanced information processing terminal device and electric automobile, extremely people's concern.
Aspect lithium ion battery, although the energy density of commercial lithium ion battery has reached 150～200W h/kg at present, but it is still subject to the restriction of traditional positive electrode and the theoretical lithium storage content limit of carbon negative pole material self, be difficult to further improve its energy density.Therefore, people turn to new high-energy-density electrode material system and the high-energy density lithium secondary cell system based on new principle by sight, as lithium-sulfur cell, sodium-sulfur battery, lithium-air battery etc.But how steadily controlling the electrochemical reaction of these high energy system, guarantee Efficient Conversion and the storage of energy, is the huge challenge of current this field face, the practical exploitation of depending on high performance electrode material of these novel secondary batteries.The secondary cell of extensive use in mobile phone and notebook computer is at present lithium ion battery, and its positive pole is mainly lithium transition-metal oxide, comprises the cobalt acid lithium (LiCoO of layer structure
2), the LiMn2O4 (LiMn of spinel structure
2o
4) and the LiFePO 4 (LiFePO of olivine structural
4) energy density is lower, is about 120～150Wh/kg, and has certain potential safety hazard, hinders its extensive use in electrokinetic cell.Lithium-sulphur and sodium-sulfur rechargeable battery are respectively to using lithium metal and sodium as negative pole, elemental sulfur or sulfenyl composite material are as anodal secondary cell, its theoretical energy density is 2600Wh/kg, actual energy density can reach 300Wh/kg at present, is considered to one of secondary cell system of current tool research attraction.In addition, elemental sulfur has cheap and advantages of environment protection and can make it have more practical value.Visible, lithium-sulphur and sodium-sulfur rechargeable battery can meet four aspects in following electrokinetic cell requirement preferably, i.e. high-energy-density, fail safe preferably, environmental protection and low cost; Weak point is that sulfenyl positive electrode all exists cycle performance poor, has restricted the development of lithium-sulphur and sodium-sulfur rechargeable battery, and this is also the emphasis of current lithium-sulphur and the research of sodium-sulfur rechargeable battery.Anodal for sulfenyl, the key issue of existence is as follows: (1) elemental sulfur is at room temperature electronics and ion insulator, while making electrode, need add a large amount of conductive agent (as acetylene black), causes the energy density of electrode system to reduce; (2) elemental sulfur can be reduced into the polysulfide of Yi Rong in discharge process, causes active material to run off, and polysulfide is dissolved in after electrolyte, can increase concentration of electrolyte, worsens its ionic conductivity; (3) be dissolved in the direct contacting metal cathode of lithium of polysulfide of electrolyte, self discharge reaction occurs; (4) in charge and discharge process can there is corresponding pucker & bloat in sulfur electrode, destroy to a certain extent the physical structure of electrode. these problems have all restricted the chemical property of sulfenyl positive pole, cause that sulphur active material utilization is low, electrochemical reversibility is poor and capacity attenuation fast etc.2009, the reports such as Nazar seminar of Canada Waterloo university, sulphur is filled in the duct of mesoporous carbon by solution osmosis, can improve the conductivity of sulphur, reduce to a certain extent dissolving (X.Ji, the K.T.Lee of polysulfide in electrolyte, L.F.Nazar, Nat.Mater.2009,8,500).From the experimental result of having reported, by sulphur solution wet method, be penetrated into carbon/sulphur composite material prepared by mesoporous carbon and can improve the chemical property of sulphur, but exist following two shortcomings urgently to overcome.Shortcoming one is that carbon/sulphur combination electrode material capacity attenuation in cyclic process of preparation is very fast, and as discharged and recharged through 20 times, capacity has decayed more than 10%.Shortcoming two be mesoporous carbon/sulphur composite material of preparing in this way containing active material---the amount of sulphur is less, cause the total capacity of electrode on the low side.For example, in this mesoporous carbon/sulphur combination electrode material, sulfur content only has 30% left and right, and the sulfenyl electrode circulation total capacity of preparation is about about 200mAh/g, far below the theoretical capacity of sulphur, only suitable with the capacity of traditional anode material for lithium-ion batteries.The performance that these two shortcomings have not only hindered material Potential performance, has also brought certain limitation to practical application.So a kind of stable, active material---sulfur content is high, and the electrode material that sulphur is difficult for running off in electrolyte is extremely to have practicality.
Summary of the invention
The present invention to achieve these goals, has adopted following structure:
The invention provides a kind of electrode material, it is characterized in that, have: permeability carbon base body and nano metal polysulfide.Wherein, nano metal polysulfide is filled in the micropore of permeability carbon base body.Electrode material sulfur content is greater than 50%.
Further, in electrode material of the present invention, can also there is such feature: wherein, the pore size of micropore is between 2nm-10nm.
Further, in electrode material of the present invention, can also there is such feature: wherein, permeability carbon base body can adopt any one material in mesoporous carbon, porous carbon, Graphene, activated carbon and foamy carbon.
Further, in electrode material of the present invention, can also there is such feature: wherein, the metal component of nano metal polysulfide is any one in Ti, V, Ni, Cu, Cr, Co, Fe, Zn, Mn, Mo and Zr.
Further, in electrode material of the present invention, can also there is such feature: wherein, the specific area of permeability carbon base body is greater than 1000m
2/ g.
The present invention also provides a kind of preparation method of electrode material, it is characterized in that:
Step 1: slaine is dissolved in water, and the metal salt solution making is dry after being loaded in permeability carbon base body by infiltration technology.
Step 2: obtain from step 1 the carbon base body that load has slaine, after reduction reaction, make the carbon base body that load has nano-metal particle.
Step 3: have the carbon base body of nano metal to drip the carbon disulfide solution for preparing in advance sulfur-bearing toward load, reaction, removes solvent by drying process, makes electrode material.
Further, in the preparation method of electrode material of the present invention, can also there is such feature:
Wherein, infiltration technology is ultrasonic assisted solution wet method.
Further, in the preparation method of electrode material of the present invention, can also there is such feature: wherein, drying process is low temperature drying flow process.
Effect and the effect of invention
According to electrode material of the present invention, different from conventional electrode material, this electrode material is that nano metal stabilisation sulphur is filled in the composite material in the micropore of permeability carbon base body, and the sulfur content in this kind of material is greater than 50%, make that wherein active component is higher, battery utilance is higher.
Nano metal stabilisation sulphur composite material is as the electrode material of lithium-sulphur and sodium-sulfur rechargeable battery, have advantages of that capacity is high, high rate capability and good cycling stability, and due to nano metal stabilisation sulphur stable in properties, can not be dissolved in electrolyte, causing active material---the loss of sulphur, reduces the utilance of battery.Its excellent specific property, is more conducive to it and is used as lithium-sulphur and sodium-sulfur battery positive electrode.By nano metal, stablize the combination electrode material that sulphur forms in carbon base body, not only can improve the cycle performance of electrode material, and its high rate capability is also improved.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope digital picture of electrode material of the present invention in embodiment 1;
Fig. 2 is the thermogravimetric analysis collection of illustrative plates of electrode material of the present invention in embodiment 1;
Fig. 3 is the curve chart of electrode material of the present invention capacitance and cycle-index in embodiment 1; And
Fig. 4 is electrode material of the present invention collection of illustrative plates of discharge capacity and cycle-index under different current densities in embodiment 1.
Embodiment
Below, with reference to accompanying drawing, electrode material involved in the present invention is elaborated.
< embodiment mono->
Embodiment 1 adopts Nanometer Copper stabilisation sulphur composite material as electrode material, and porous carbon is carbon base body.Wherein, sulfur content surpasses 50%, and the micropore of porous carbon is used for holding Nanometer Copper stabilisation sulphur.The aperture of micropore is 5nm, and the specific area of porous carbon is 1100m
2/ g.
Fig. 1 is the transmission electron microscope digital picture of electrode material of the present invention.
As shown in Figure 1, can observe in permeability carbon base body and exist nano metal polysulfide, nano metal polysulfide to fill the micropore in carbon base body.
Fig. 2 is the thermogravimetric analysis collection of illustrative plates of electrode material of the present invention;
As shown in Figure 2, electrode material starts to decline 200 ° of-300 ° of its weight, and when temperature approaches 500 °, its weight reaches balance, this kind of electrode material better heat stability.
Fig. 3 is the curve chart of electrode material capacitance of the present invention and cycle-index.
As shown in Figure 3, in loop test, electrode material has higher discharge capacity, and its charging capacity and discharge capacity ratio be 100%, and efficiency is higher.Even after 500 charge and discharge cycles, capacity still remains on 600mAh/g, demonstrate high power capacity and excellent high rate capability.
Fig. 4 is the collection of illustrative plates of electrode material of the present invention discharge capacity and cycle-index under different current densities.
As shown in Figure 4, in loop test, the discharge capacity of electrode material is along with different current densities are successively decreased step by step, and when current density increases suddenly, electrode material does not still have destroyed, illustrates that this electrode material is superior, and stable circulation performance is good.The Nanometer Copper making stablize sulphur in the combination electrode material of carbon base body under high current charge-discharge condition, still there is high capacity, as when 10A/g discharges and recharges, electrode capacity is in 200mAh/g left and right.
The effect of embodiment 1 and effect
According to electrode material of the present invention, different from conventional electrode material, this electrode material is that Nanometer Copper stabilisation sulphur is filled in the composite material in the micropore of permeability carbon base body, and the sulfur content in this kind of material is greater than 50%, make that wherein active component is higher, battery utilance is higher.
Nanometer Copper stabilisation sulphur composite material is as the electrode material of lithium-sulphur and sodium-sulfur rechargeable battery, have advantages of that capacity is high, high rate capability and good cycling stability, and due to Nanometer Copper stabilisation sulphur stable in properties, can not be dissolved in electrolyte, causing active material---the loss of sulphur, reduces the utilance of battery.Its excellent specific property, is more conducive to it and is used as lithium-sulphur and sodium-sulfur battery positive electrode.By Nanometer Copper, stablize the combination electrode material that sulphur forms in carbon base body, not only can improve the cycle performance of electrode material, and its high rate capability is also improved.
In addition, because the aperture of micropore is 5nm, therefore can better hold Nanometer Copper stabilisation sulphur.
In addition, the specific area due to porous carbon is 1100m
2/ g, therefore can hold more Nanometer Copper stabilisation sulphur.
< embodiment bis->
The present embodiment provides the preparation method of Nanometer Copper stabilisation sulphur combination electrode material in embodiment mono-, and its concrete steps are as follows:
Step 1: copper nitrate is carried on to permeability carbon base body
At room temperature, the ratio that is 1:10 in copper content/porous carbon amount, calculates weight, accurately weighs copper nitrate and porous carbon, and copper nitrate is soluble in water, after being loaded in permeability carbon base body by ultrasonic auxiliary infiltration, and 100 ℃ of vacuumizes.
Step 2: carry out hydrogen reduction reaction
The load that step 1 is obtained has the porous carbon of copper nitrate, at 400 ℃, passes into hydrogen reducing reaction 5 hours, makes the porous carbon that load has nano copper particle.
Step 3, the porous carbon that is loaded with Nanometer Copper that step 2 is obtained, by weight 1:2, drip the carbon disulfide solution of the sulfur content 50% preparing in advance, then at 60 ℃, solvent is removed in vacuumize, obtains sulfur content and surpasses 50% Nanometer Copper stabilisation sulphur composite material.
The slaine that the present invention selects is copper nitrate; The material with carbon element of selecting is high specific surface area porous carbon, and specific area is at 1100m
2/ g left and right, aperture is 5nm.
Further the Nanometer Copper making is stablized to sulphur and carry out electrochemical property test in porous carbon composite material, in lithium-sulfur cell, demonstrate high power capacity and excellent high rate capability, even after 500 charge and discharge cycles, capacity still remains on 600mAh/g.
< embodiment tri->
This embodiment is that high power capacity, high magnification and the good nano nickel of stable circulation performance are stablized sulphur in the preparation method of mesoporous carbon composite electrode material, and concrete steps are as follows:
Step 1: nickel chloride is carried on mesoporous carbon matrix
At room temperature, the ratio that is 1:10 in nickel content/mesoporous carbon amount, calculates weight, accurately weighs nickel chloride and mesoporous carbon, and nickel chloride is soluble in water, after being loaded in mesoporous carbon matrix by ultrasonic auxiliary infiltration, and 100 ℃ of vacuumizes.
Step 2: hydrogen reduction reaction
The load that step 1 is obtained has the mesoporous carbon of nickel chloride, at 400 ℃, passes into hydrogen reducing reaction 5 hours, makes the mesoporous carbon that load has nano nickle granules.
Step 3: the mesoporous carbon that is loaded with nano nickel that step 2 is obtained, the carbon disulfide solution of the sulfur content 50% preparing in advance by weight 1:2 dropping, then at 60 ℃, solvent is removed in vacuumize, the nano nickel stabilisation sulphur composite material obtaining.
The slaine that the present invention selects is nickel chloride; The material with carbon element of selecting is mesoporous carbon, and specific area is at 1200m
2/ g left and right, aperture is at 4nm.
The nano nickel of above-mentioned gained is stablized to sulphur and in mesoporous carbon composite electrode material, adopt multichannel cell tester (CT2001A, Wuhan City Lan electricity electronics limited company, China) carry out electrochemical property test, electrode is after more than 300 charge and discharge cycles, more than discharge capacity continues to remain on 600mAh/g, and except 1-2 time initial activation cycle, efficiency for charge-discharge maintains 100% all the time.
The nano nickel of above-mentioned gained is stablized to sulphur and in mesoporous carbon composite electrode material, adopt multichannel cell tester (CT2001A, Wuhan City Lan electricity electronics limited company, China) carry out the test of different current discharge properties, the nano nickel making is stablized sulphur combination electrode material under high current charge-discharge condition, still there is high capacity, under the charging and discharging currents up to 10A/g, electrode discharge capacity still can reach 200mAh/g.
< embodiment tetra->
This embodiment is that high power capacity, high magnification and the good nanometer cobalt of stable circulation performance are stablized sulphur in the preparation method of foamy carbon combination electrode material, and concrete steps are as follows:
Step 1: cobalt nitrate is carried on foamy carbon matrix
At room temperature, in the ratio that is 1:10 containing cobalt amount/foamy carbon amount, calculate weight, accurately weigh cobalt nitrate and porous carbon, cobalt nitrate is soluble in water, after being loaded in foamy carbon matrix by ultrasonic auxiliary infiltration, 100 ℃ of vacuumizes.
Step 2: hydrogen reduction reaction
The load that step 1 is obtained has the foamy carbon of cobalt nitrate, at 400 ℃, passes into hydrogen reducing reaction 5 hours, makes the foamy carbon that load has nano cobalt granule.
Step 3: the foamy carbon that is loaded with nanometer cobalt that step 2 is obtained, the carbon disulfide solution of the sulfur-bearing 50% preparing in advance by weight 1:2 dropping, then at 60 ℃, solvent is removed in vacuumize, the nanometer cobalt stabilisation sulphur composite material obtaining.
The slaine that the present invention selects is cobalt nitrate; The material with carbon element of selecting is high-specific surface area foamy carbon, and specific area is at 1300m
2/ g left and right.Aperture is 4nm.
The nanometer cobalt of above-mentioned gained is stablized to sulphur and in porous carbon combination electrode material, adopt multichannel cell tester (CT2001A, Wuhan City Lan electricity electronics limited company, China) carry out electrochemical property test, electrode is after more than 400 charge and discharge cycles, electrode capacity continues to remain on 600mAh/g left and right, and except 1-2 time initial activation cycle, efficiency for charge-discharge maintains 100% all the time.
The nanometer cobalt of above-mentioned gained is stablized to sulphur and in porous carbon combination electrode material, adopt multichannel cell tester (CT2001A, Wuhan City Lan electricity electronics limited company, China) carry out the test of different current discharge properties, the nanometer cobalt making is stablized sulphur combination electrode material under high current charge-discharge condition, still there is high capacity, under the charging and discharging currents up to 10A/g, electrode discharge capacity still can reach 200mAh/g.
Effect and the effect of embodiment bis-to four
The preparation method of the nano metal stabilisation sulphur combination electrode material that embodiment bis-to four provides, adopted respectively copper, nickel and cobalt, and permeability carbon base body has adopted respectively porous carbon, mesoporous carbon and foamy carbon, easy and simple to handle efficient, after the salting liquid of above-mentioned metal can being loaded into permeability carbon base body by infiltration technology, be dried, by the reaction of hydrogen heat reduction, make the nanometer sized metal particles loading on carbon base body, drip the carbon disulfide solution of the sulphur preparing in advance, then the nano metal stabilisation sulphur composite material making by dry removal solvent, sulfur content in permeability carbon base body can be brought up to the degree that surpasses 50%, industrial, there is practicality.
In addition, the nano metal of this electrode material is not limited only to Cu, Ni and the Co that above-described embodiment is mentioned, with the salting liquid of the transition metal such as Ti, V, Cr, Fe, Zn, Mn, Mo, Zr, all can realize its effect, the carbon base body of this electrode material is also not limited only to mesoporous carbon, porous carbon and the foamy carbon that above-described embodiment is mentioned, and other specific areas are greater than 1000m
2the permeability material with carbon element of/g can permeate and hydrogen reduction reaction is prepared nano metal and stablize sulphur in carbon base body combination electrode material, lithium-sulphur and sodium-sulfur rechargeable battery electrode material of the nano metal stabilisation sulphur that acquisition high power capacity, high magnification and stable circulation performance are good by wet method equally.Reduction temperature is not limited only to 400 ℃, and reduction temperature all can be realized the effect that slaine is reduced into completely to nano metal at 300 ℃-500 ℃.
Certainly electrode material involved in the present invention and preparation method thereof is not merely defined in structure in the above-described embodiments.Above content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (8)
1. an electrode material, is characterized in that, has:
Permeability carbon base body and nano metal polysulfide,
Wherein, described nano metal polysulfide is filled in the micropore of described permeability carbon base body,
Described electrode material sulfur content is greater than 50%.
2. electrode material according to claim 1, is characterized in that:
Wherein, the pore size of described micropore is between 2nm-10nm.
3. electrode material according to claim 1, is characterized in that:
Wherein, described permeability carbon base body can adopt any one material in mesoporous carbon, porous carbon, Graphene, activated carbon and foamy carbon.
4. electrode material according to claim 1, is characterized in that:
Wherein, the metal component of described nano metal polysulfide is any one in Ti, V, Ni, Cu, Cr, Co, Fe, Zn, Mn, Mo and Zr.
5. electrode material according to claim 1, is characterized in that:
Wherein, the specific area of described permeability carbon base body is greater than 1000m
2/ g.
6. a preparation method for electrode material as claimed in claim 1, is characterized in that:
Step 1: slaine is dissolved in water, and the metal salt solution making is dry after being loaded in permeability carbon base body by infiltration technology;
Step 2: obtain from step 1 the carbon base body that load has slaine, after reduction reaction, make the carbon base body that load has nano-metal particle;
Step 3: have the carbon base body of nano metal to drip the carbon disulfide solution for preparing in advance sulfur-bearing toward described load, reaction, removes solvent by drying process, makes described electrode material.
7. preparation method according to claim 6, is characterized in that:
Wherein, described infiltration technology is ultrasonic assisted solution wet method.
8. preparation method according to claim 6, is characterized in that:
Wherein, described drying process is low temperature drying flow process.
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| WO2016057619A1 (en) | 2014-10-08 | 2016-04-14 | Wayne State University | Electrocatalysis of lithium polysulfides: current collectors as electrodes in li/s battery configuration |
| CN106848254A (en) * | 2017-03-20 | 2017-06-13 | 上海中聚佳华电池科技有限公司 | A kind of anode material of lithium-ion battery and preparation method thereof, sodium-ion battery |
| CN109273676A (en) * | 2018-08-16 | 2019-01-25 | 浙江大学 | A kind of sulphur-mycotic spore carbon ball/phosphide composite material and preparation method and application |
| CN111224082A (en) * | 2019-12-02 | 2020-06-02 | 大连理工大学 | Copper/porous carbon material capable of being used as lithium-sulfur battery anode carrier material, preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106848254A (en) * | 2017-03-20 | 2017-06-13 | 上海中聚佳华电池科技有限公司 | A kind of anode material of lithium-ion battery and preparation method thereof, sodium-ion battery |
| CN106848254B (en) * | 2017-03-20 | 2020-09-01 | 上海中聚佳华电池科技有限公司 | Sodium-ion battery negative electrode material, preparation method thereof and sodium-ion battery |
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| CN111224082A (en) * | 2019-12-02 | 2020-06-02 | 大连理工大学 | Copper/porous carbon material capable of being used as lithium-sulfur battery anode carrier material, preparation method and application |
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