CN109980212A - A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method - Google Patents

A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method Download PDF

Info

Publication number
CN109980212A
CN109980212A CN201910333138.6A CN201910333138A CN109980212A CN 109980212 A CN109980212 A CN 109980212A CN 201910333138 A CN201910333138 A CN 201910333138A CN 109980212 A CN109980212 A CN 109980212A
Authority
CN
China
Prior art keywords
ion battery
sodium
negative pole
composite negative
pole material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910333138.6A
Other languages
Chinese (zh)
Inventor
黄剑锋
何元元
曹丽云
李嘉胤
党欢
李倩颖
刘倩倩
仵婉晨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201910333138.6A priority Critical patent/CN109980212A/en
Publication of CN109980212A publication Critical patent/CN109980212A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method, glucose is dissolved in EtOH-DI water in the mixed solvent and obtains precursor solution: nickel foam and precursor solution being added in reaction kettle and carry out hydro-thermal reaction, after reaction, cooled to room temperature, product is washed, is dried, product after drying is carried out to be heat-treated to obtain target product, by target product FeCl3The nickel that defoams is handled with HCl solution, obtains final product after washing, dry and grinding.Composite negative pole material prepared by the present invention has the good electric conductivity of soft carbon (graphitic carbon) and the high capacity of hard carbon (agraphitic carbon), for showing excellent performance when anode material of lithium-ion battery.The raw materials used stable components of this method, from a wealth of sources, technological operation is simple, is conducive to industrialized production.

Description

A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method
Technical field
The present invention relates to a kind of preparation methods of anode material of lithium-ion battery, and in particular to a kind of sodium-ion battery is with soft Carbon-hard carbon composite negative pole material preparation method.
Background technique
Electrochemical energy energy storage technology not only facilitates clean energy resource of the storage from renewable energy, reduces to fossil fuel The dependence of consumption, but also can the significant discharge for reducing greenhouse gases.In different electrochemical energy energy storage technologies, lithium-ion electric Pond is still the choosing of portable electronic device and certain electric vehicles due to its high-energy/power density and long cycle life It selects.However, due to rarity and geographic, the uneven distribution of the worry lithium resource of large scale deployment lithium ion battery People are caused increasingly to pay attention to the important replacement of lithium ion battery: sodium-ion battery.Based on the alkali similar with lithium ion battery Metallochemistry, sodium-ion battery show that it is expected to the solution as power grid grade electrochemical energy energy storage technology.This and sodium resource Low cost, enrich it is related with sustainability advantage brought by wide usability.
Graphite is the most realistic selection of lithium ion battery, and for sodium-ion battery, its capacity is lower.It is candidate in various anodes In object, hard carbon anode has attracted most concerns.Nearest 2 years, sodium-ion battery field obtained in terms of Carbon anode significantly at Fruit.Carbon material is lower due to environmental-friendly, resourceful, nontoxic, highly-safe, thermal stability and price, it has also become most inhales One of candidate material of gravitation.A large amount of carbon nanomaterial is had reported at present as anode material of lithium-ion battery, including hard (Xu Kaiqi, Su Wei, Zhong Guobin wait the Guangdong progress [J] the electricity of the first all efficiency of sodium-ion battery hard carbon cathode material to carbon Power, 2018 (2)), carbon black (Alc á ntara R, Jim é nez-Mateos J M, Lavela P, et al.Carbon black: a promising electrode material for sodium-ion batteries[J].Electrochemistry Communications, 2001,3 (11): 639-642.), carbon fiber (Zhu Y, Han X, Xu Y, et al.Electrospun Sb/C fibers for a stable and fast sodium-ion battery anode[J].Acs Nano,2013,7 (7): 6378-6386.), (Li Huan, Cao Xiaoyan, Han Xiaoqi wait the electrochemical process of sodium-ion battery expanded graphite to expanded graphite Preparation and performance probe into [J] functional material, 2016,47 (12): 12162-12168.) and graphene (Yan Y, Yin Y X, Guo Y G,et al.A Sandwich-Like Hierarchically Porous Carbon/Graphene Composite as a High-Performance Anode Material for Sodium-Ion Batteries[J].Advanced Energy Materials,2014,4(8):1079-1098.).In all Carbon anode candidates, since high electrochemical is living Property and relatively low cost, amorphous carbon (such as hard carbon and soft carbon) cause great concern.Hard carbon contains a large amount of unordered knot Structure has defect and gap, is conducive to high reversible capacity, but have biggish initial irreversible capacity, and the nothing in hard carbon Sequence structure causes electronic conductivity low, leads to the performance of difference.Compared with not graphitisable hard carbon, soft carbon represents graphitisable Carbon, degree of graphitization and interfloor distance can be adjusted by being heat-treated.Soft carbon has graphite area abundant, and defect is relatively It is few, cause conductivity high, Initial Coulombic Efficiencies are low.How these advantages to be focused in a kind of material, by soft carbon and hard carbon " organic " be incorporated on a material, realize cycle performance and the excellent soft or hard carbon compound cathode of sodium-ion battery of high rate performance Material is advantageously implemented the commercialization of sodium-ion battery.
Summary of the invention
The purpose of the present invention is to provide a kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method, Prepared composite negative pole material has the high capacity of the good electric conductivity and hard carbon (agraphitic carbon) of soft carbon (graphitic carbon) simultaneously, Not only enable battery long-term work, but also intermittent energy source quick storage can be better met, promotes battery apparatus Storage efficiency.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
1) glucose is dissolved in the in the mixed solvent of ethyl alcohol and deionized water, is sufficiently stirred, before obtaining 0.02-0.1mol/L Drive liquid solution；
2) nickel foam and precursor solution are added in reaction kettle, in 160~220 DEG C of progress hydro-thermal reactions；
3) after reaction, cooled to room temperature, and product is washed, is dried；
4) product of step 3) is placed in heat treatment under 600~900 DEG C of inert atmospheres and obtains target product；
5) by target product FeCl3The nickel that defoams is handled with HCl solution, it is compound to obtain soft carbon-hard carbon after washing is dry Negative electrode material.
The mixed solvent ethyl alcohol of the step 1) and the volume ratio of deionized water are 1:1.
The long 4cm of the nickel foam of the step 2), width 3.0cm, thickness 1.0mm.
The nickel foam of the step 2) is successively through deionized water, acetone, the hydrochloric acid and EtOH Sonicate that concentration is 1-5mol/L 30-60min, 30-60min, 5-10min and 30-60min are cleaned, then in 60-100 DEG C of vacuum drying 6-12h.
The reaction kettle of the step 2) is polytetrafluoroethyllining lining.
The hydro-thermal reaction time of the step 2) be 12~for 24 hours.
The washing of the step 3) uses one or both of deionized water and dehydrated alcohol, acetone to clean 3~6 respectively It is secondary, in the dry 6-12h of 80-120 DEG C of vacuum oven.
The inert atmosphere of the step 4) is argon atmosphere.
The heat treatment of the step 4) is the heating speed being placed in the product of step 3) in ceramic crucible with 3~10 DEG C/min Rate is from room temperature to 600~900 DEG C of 1~3h of heat treatment.
The FeCl of the step 5) 0.5-3.0mol/L3With the HCl solution magnetic agitation 12-24h of 1.0-3.0mol/L Defoam nickel, dry in 60-120 DEG C of vacuum oven after then respectively washing 3~5 times using deionized water and dehydrated alcohol 6-12h。
The present invention is prepared for sodium-ion battery with soft using efficient, simple hydro-thermal method combination inert gas heat treatment method Carbon-hard carbon composite negative pole material.Soft carbon-hard carbon composite negative pole material excellent properties not only enable battery long-term work, And intermittent energy source quick storage can be better met, promote the storage efficiency of battery apparatus.It is provided for extensive energy storage A possibility that a kind of new.
Carbon source of the present invention is glucose, is had many advantages, such as environmental-friendly, from a wealth of sources, cheap and easy to get.This hair It is bright to synthesize final product using hydro-thermal method combination inert gas heat treatment method.Used preparation method is simple, is easy to grasp Make, and does not need large scale equipment and harsh reaction condition, it is highly-safe, it is suitble to large-scale production.
The present invention grows hard carbon material by hydro-thermal method in nickel foam, by metallic nickel in follow-up heat treatment process to hard The catalyzed graphitization of carbon material acts on, so that the hard carbon with nickel foam contact portion is converted into soft carbon (graphitized carbon), thus To the carbon negative pole material compound by soft or hard carbon, soft carbon (graphitized carbon) work therein when it is as anode material of lithium-ion battery It for electron transfer layer, can effectively accelerate electron conductivity, improve high rate performance, and hard carbon material is conducive to as storage sodium matrix Sodium ion insertion and abjection.Soft or hard carbon composite can be effectively improved the capacity of Carbon negative electrode material of sodium ion battery and forthright again Energy.
Detailed description of the invention
Fig. 1 is sodium-ion battery soft carbon-hard carbon composite negative pole material X-ray diffraction prepared by the embodiment of the present invention 1 Analysis chart；
Fig. 2 is sodium-ion battery soft carbon-hard carbon composite negative pole material Raman figure prepared by the embodiment of the present invention 2；
Fig. 3 is sodium-ion battery soft carbon-hard carbon composite negative pole material SEM spectrum prepared by the embodiment of the present invention 3；
Fig. 4 is sodium-ion battery soft carbon-hard carbon composite negative pole material SEM spectrum prepared by the embodiment of the present invention 1；
Fig. 5 is sodium-ion battery soft carbon-hard carbon composite negative pole material TEM map prepared by the embodiment of the present invention 4.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and embodiments, but the present invention is not limited to following implementation Example.
Embodiment 1:
1) glucose is dissolved in the in the mixed solvent of the ethyl alcohol that volume ratio is 1:1 and deionized water, is sufficiently stirred, obtains 0.02mol/L precursor solution；
2) take the nickel foam of long 4cm, width 3.0cm, thickness 1.0mm successively through deionized water, acetone, the salt that concentration is 2mol/L Acid and EtOH Sonicate clean 30min, 50min, 8min and 40min, then in 80 DEG C of vacuum drying 9h, nickel foam presoma is molten Liquid is added in the reaction kettle of polytetrafluoroethyllining lining, in 180 DEG C of hydro-thermal reaction 18h；
3) after reaction, cooled to room temperature is cleaned 6 times with deionized water and anhydrous second respectively, in 80 DEG C of vacuum Drying box dries 12h；
4) by the product of step 3) be placed in ceramic crucible with the heating rate of 5 DEG C/min from room temperature to 800 DEG C It is heat-treated 1h under argon atmosphere and obtains target product；
5) by the FeCl of target product 3.0mol/L3It defoams nickel with the HCl solution magnetic agitation 12h of 1mol/L, Then it is respectively washed 5 times using deionized water and dehydrated alcohol, it is compound to obtain soft carbon-hard carbon by dry 6h in 120 DEG C of vacuum ovens Negative electrode material.
X-ray diffraction (XRD) figure of prepared soft or hard carbon compound cathode materials shows (002) as seen from Figure 1 (100) two weak wide diffraction maximums, show its amorphous property.It is worth noting that its (002) peak position is set to~25 °, it is right Interfloor distance (the d answered002, it is calculated according to Bragg's equation) and it is 0.355nm.Interfloor distance is slightly larger than the interlamellar spacing of graphite From (0.335nm).Lesser interlamellar spacing possibly can not be embedded in sodium ion, and the conduction of electronics is influenced by graphitic carbon degree.
As seen from Figure 4 in the SEM figure of prepared soft or hard carbon compound cathode materials, sample mainly by diameter not Deng carbon ball interconnected composition, carbon ball diameter is distributed as 800nm~2 μm.
Embodiment 2:
1) glucose is dissolved in the in the mixed solvent of the ethyl alcohol that volume ratio is 1:1 and deionized water, is sufficiently stirred, obtains 0.04mol/L precursor solution；
2) take the nickel foam of long 4cm, width 3.0cm, thickness 1.0mm successively through deionized water, acetone, the salt that concentration is 2mol/L Acid and EtOH Sonicate clean 40min, 60min, 5min and 50min, then in 100 DEG C of vacuum drying 6h, by nickel foam presoma Solution is added in the reaction kettle of polytetrafluoroethyllining lining, in 200 DEG C of hydro-thermal reaction 12h；
3) after reaction, cooled to room temperature is cleaned 6 times with deionized water and acetone respectively, dry in 100 DEG C of vacuum The dry 9h of dry case；
4) by the product of step 3) be placed in ceramic crucible with the heating rate of 3 DEG C/min from room temperature to 700 DEG C It is heat-treated 2h under argon atmosphere and obtains target product；
5) by the FeCl of target product 2.5mol/L3It defoams nickel with the HCl solution magnetic agitation 12h of 2mol/L, Then it is respectively washed 3 times using deionized water and dehydrated alcohol, it is compound to obtain soft carbon-hard carbon by dry 12h in 60 DEG C of vacuum ovens Negative electrode material.
There are two of D band and G band in the Raman spectrum of prepared soft or hard carbon compound cathode materials as seen from Figure 2 Independent characteristic peak is located at~1346cm-1 and~1591cm-1.The peak D, which corresponds to sp3 hydridization carbon, has disordered state and G Peak corresponds to the sp2 hydridization carbon with graphite-structure.The integrated intensity ratio (IG/ID) at the peak G and the peak D can be used for assessing graphitization journey Degree, higher IG/ID value indicate more graphite-structures, and high degree of graphitization indicates high conductivity.Raman fitting The result shows that prepared sample degree of graphitization with higher, this is conducive to the electric charge transfer during electrochemical reaction.
Embodiment 3:
1) glucose is dissolved in the in the mixed solvent of the ethyl alcohol that volume ratio is 1:1 and deionized water, is sufficiently stirred, obtains 0.06mol/L precursor solution；
2) take the nickel foam of long 4cm, width 3.0cm, thickness 1.0mm successively through deionized water, acetone, the salt that concentration is 3mol/L Acid and EtOH Sonicate clean 50min, 30min, 10min and 60min, then in 90 DEG C of vacuum drying 8h, by nickel foam presoma Solution is added in the reaction kettle of polytetrafluoroethyllining lining, in 220 DEG C of hydro-thermal reaction 12h；
3) after reaction, cooled to room temperature uses deionized water and washes of absolute alcohol 6 times respectively, true at 90 DEG C The dry 8h of empty drying box；
4) by the product of step 3) be placed in ceramic crucible with the heating rate of 7 DEG C/min from room temperature to 900 DEG C It is heat-treated 1h under argon atmosphere and obtains target product；
5) by the FeCl of target product 2mol/L3It defoams nickel with the HCl solution magnetic agitation 12h of 1mol/L, so It is respectively washed 4 times using deionized water and dehydrated alcohol afterwards, dry 9h obtains soft carbon-hard carbon composite negative pole in 90 DEG C of vacuum ovens Material.
As seen from Figure 3 in the SEM figure of prepared soft or hard carbon compound cathode materials, sample is by carbon shell and is attached to carbon Carbon ball composition on shell.A large amount of height carbon ball diameters interconnected are about 1 μm, carbon shell with a thickness of~600nm.Carbon shell and bubble The contact of foam nickel is catalyzed into as soft carbon, and carbon ball then retains original hard carbon feature.The lesser solid phase hard carbon shell of thickness can reduce Na+ Diffusion path.
Embodiment 4:
1) glucose is dissolved in the in the mixed solvent of the ethyl alcohol that volume ratio is 1:1 and deionized water, is sufficiently stirred, obtains 0.08mol/L precursor solution；
2) take the nickel foam of long 4cm, width 3.0cm, thickness 1.0mm successively through deionized water, acetone, the salt that concentration is 1mol/L Acid and EtOH Sonicate clean 60min, 45min, 6min and 30min, then in 60 DEG C of vacuum drying 12h, by nickel foam presoma Solution is added in the reaction kettle of polytetrafluoroethyllining lining, 180 DEG C of hydro-thermal reactions for 24 hours；
3) after reaction, cooled to room temperature is cleaned 6 times with deionized water and acetone respectively, dry in 120 DEG C of vacuum The dry 6h of dry case；
4) by the product of step 3) be placed in ceramic crucible with the heating rate of 3 DEG C/min from room temperature to 600 DEG C It is heat-treated 3h under argon atmosphere and obtains target product；
5) by the FeCl of target product 1.5mol/L3It defoams nickel with the HCl solution magnetic agitation 12h of 3mol/L, Then it is respectively washed 5 times using deionized water and dehydrated alcohol, it is compound to obtain soft carbon-hard carbon by dry 8h in 100 DEG C of vacuum ovens Negative electrode material.
The high resolution transmission electron microscope of prepared soft or hard carbon compound cathode materials as seen from Figure 5 (HRTEM) figure, which is shown in after the catalysis of metal foam nickel, generates fold stratiform graphitic carbon, and the interfloor distance of graphitic carbon is~ 0.355nm.Widened interlamellar spacing is unfavorable for the diffusion and storage of sodium ion, but enhances the electric conductivity of hard carbon, therefore ensure that The fast transferring of electronics is to improve high rate performance.
Embodiment 5:
1) glucose is dissolved in the in the mixed solvent of the ethyl alcohol that volume ratio is 1:1 and deionized water, is sufficiently stirred, obtains 0.08mol/L precursor solution；
2) take the nickel foam of long 4cm, width 3.0cm, thickness 1.0mm successively through deionized water, acetone, the salt that concentration is 5mol/L Acid and EtOH Sonicate clean 45min, 55min, 7min and 35min, then in 70 DEG C of vacuum drying 10h, by nickel foam presoma Solution is added in the reaction kettle of polytetrafluoroethyllining lining, in 180 DEG C of hydro-thermal reaction 12h；
3) after reaction, cooled to room temperature is cleaned 5 times with deionized water, dehydrated alcohol and acetone respectively, The dry 7h of 110 DEG C of vacuum ovens；
4) by the product of step 3) be placed in ceramic crucible with the heating rate of 5 DEG C/min from room temperature to 900 DEG C It is heat-treated 2h under argon atmosphere and obtains target product；
5) by the FeCl of target product 1mol/L3It defoams for 24 hours nickel with the HCl solution magnetic agitation of 2mol/L, so It is respectively washed 4 times using deionized water and dehydrated alcohol afterwards, dry 10h obtains soft carbon-hard carbon Compound Negative in 80 DEG C of vacuum ovens Pole material.
Embodiment 6:
1) glucose is dissolved in the in the mixed solvent of the ethyl alcohol that volume ratio is 1:1 and deionized water, is sufficiently stirred, obtains 0.1mol/L precursor solution；
2) take the nickel foam of long 4cm, width 3.0cm, thickness 1.0mm successively through deionized water, acetone, the salt that concentration is 2mol/L Acid and EtOH Sonicate clean 35min, 50min, 9min and 50min, then in 100 DEG C of vacuum drying 6h, by nickel foam presoma Solution is added in the reaction kettle of polytetrafluoroethyllining lining, in 160 DEG C of hydro-thermal reaction 12h；
3) after reaction, cooled to room temperature uses deionized water and washes of absolute alcohol 3 times respectively, true at 100 DEG C The dry 10h of empty drying box；
4) by the product of step 3) be placed in ceramic crucible with the heating rate of 10 DEG C/min from room temperature to 800 DEG C It is heat-treated 3h under argon atmosphere and obtains target product；
5) by the FeCl of target product 0.5mol/L3It defoams nickel with the HCl solution magnetic agitation 18h of 3mol/L, Then it is respectively washed 5 times using deionized water and dehydrated alcohol, it is compound to obtain soft carbon-hard carbon by dry 11h in 70 DEG C of vacuum ovens Negative electrode material.

Claims (10)

1. a kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method, which is characterized in that including following step It is rapid:
1) glucose is dissolved in the in the mixed solvent of ethyl alcohol and deionized water, is sufficiently stirred, 0.02-0.1mol/L presoma is obtained Solution；
2) nickel foam and precursor solution are added in reaction kettle, in 160~220 DEG C of progress hydro-thermal reactions；
3) after reaction, cooled to room temperature, and product is washed, is dried；
4) product of step 3) is placed in heat treatment under 600~900 DEG C of inert atmospheres and obtains target product；
5) by target product FeCl3The nickel that defoams is handled with HCl solution, obtains soft carbon-hard carbon composite negative pole material after washing is dry Material.
2. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In the mixed solvent ethyl alcohol of the step 1) and the volume ratio of deionized water are 1:1.
3. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In the long 4cm of the nickel foam of the step 2), width 3.0cm, thickness 1.0mm.
4. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In the nickel foam of the step 2) is successively cleaned through deionized water, acetone, the hydrochloric acid that concentration is 1-5mol/L and EtOH Sonicate 30-60min, 30-60min, 5-10min and 30-60min, then in 60-100 DEG C of vacuum drying 6-12h.
5. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In the reaction kettle of the step 2) is polytetrafluoroethyllining lining.
6. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In the hydro-thermal reaction time of, the step 2) be 12~for 24 hours.
7. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In, the washing of the step 3) uses one or both of deionized water and dehydrated alcohol, acetone to clean 3~6 times respectively, The dry 6-12h of 80-120 DEG C of vacuum oven.
8. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In the inert atmosphere of the step 4) is argon atmosphere.
9. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature exist In the heat treatment of the step 4) is to be placed in the product of step 3) in ceramic crucible with the heating rate of 3~10 DEG C/min certainly Room temperature is to 600~900 DEG C of 1~3h of heat treatment.
10. sodium-ion battery according to claim 1 soft carbon-hard carbon composite negative pole material preparation method, feature It is, the FeCl of the step 5) 0.5-3.0mol/L3It is removed with the HCl solution magnetic agitation 12-24h of 1.0-3.0mol/L Nickel foam dries 6- in 60-120 DEG C of vacuum oven after then respectively washing 3~5 times using deionized water and dehydrated alcohol 12h。
CN201910333138.6A 2019-04-24 2019-04-24 A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method Pending CN109980212A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910333138.6A CN109980212A (en) 2019-04-24 2019-04-24 A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910333138.6A CN109980212A (en) 2019-04-24 2019-04-24 A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method

Publications (1)

Publication Number Publication Date
CN109980212A true CN109980212A (en) 2019-07-05

Family

ID=67086061

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910333138.6A Pending CN109980212A (en) 2019-04-24 2019-04-24 A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method

Country Status (1)

Country Link
CN (1) CN109980212A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111755675A (en) * 2020-06-30 2020-10-09 中国石油大学(华东) Preparation method of hard and soft carbon composite material electrode for sodium/potassium electricity
CN113972359A (en) * 2021-10-21 2022-01-25 河北零点新能源科技有限公司 Preparation device and method of soft and hard carbon composite negative electrode of high-performance sodium ion battery
CN114516627A (en) * 2021-12-24 2022-05-20 宁波中车新能源科技有限公司 Preparation method of soft and hard carbon composite nano material
CN116675215A (en) * 2023-06-21 2023-09-01 湖南大学 Preparation method and application of soft carbon/hard carbon composite material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106935856A (en) * 2017-03-28 2017-07-07 中南大学 A kind of carbon-based composite negative pole material of sodium-ion battery and preparation method thereof
CN107240680A (en) * 2017-05-21 2017-10-10 合肥国轩高科动力能源有限公司 Hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof
CN108878774A (en) * 2018-06-26 2018-11-23 上海汉行科技有限公司 A kind of complex carbon material and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106935856A (en) * 2017-03-28 2017-07-07 中南大学 A kind of carbon-based composite negative pole material of sodium-ion battery and preparation method thereof
CN107240680A (en) * 2017-05-21 2017-10-10 合肥国轩高科动力能源有限公司 Hard carbon-metal oxide-soft carbon composite material and preparation method and application thereof
CN108878774A (en) * 2018-06-26 2018-11-23 上海汉行科技有限公司 A kind of complex carbon material and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANFENG HUANG等: "Constructing Conductive Graphitic Structure on Hard Carbon as an Efficient Free-Standing Anode for Sodium-Ion Batteries", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111755675A (en) * 2020-06-30 2020-10-09 中国石油大学(华东) Preparation method of hard and soft carbon composite material electrode for sodium/potassium electricity
CN111755675B (en) * 2020-06-30 2021-11-09 中国石油大学(华东) Preparation method of hard and soft carbon composite material electrode for sodium/potassium electricity
CN113972359A (en) * 2021-10-21 2022-01-25 河北零点新能源科技有限公司 Preparation device and method of soft and hard carbon composite negative electrode of high-performance sodium ion battery
CN113972359B (en) * 2021-10-21 2023-11-03 河北零点新能源科技有限公司 Preparation device and method of high-performance sodium ion battery soft and hard carbon composite negative electrode
CN114516627A (en) * 2021-12-24 2022-05-20 宁波中车新能源科技有限公司 Preparation method of soft and hard carbon composite nano material
CN116675215A (en) * 2023-06-21 2023-09-01 湖南大学 Preparation method and application of soft carbon/hard carbon composite material
CN116675215B (en) * 2023-06-21 2024-03-22 湖南大学 Preparation method and application of soft carbon/hard carbon composite material

Similar Documents

Publication Publication Date Title
CN109980212A (en) A kind of sodium-ion battery soft carbon-hard carbon composite negative pole material preparation method
CN109148884B (en) Carbon-based negative electrode material with high slope capacity and preparation method and application thereof
CN104852028A (en) Lithium titanate/graphene composite cathode material for lithium ion battery
CN106532049B (en) A kind of preparation method of porous structure sodium-ion battery carbon electrode material
CN108493403B (en) Synthesis method of self-supporting sodium ion battery cathode
CN107464938B (en) Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery
CN109873134A (en) Iron-based chalcogenide, electrode material, the sodium-ion battery and preparation method thereof of in-situ carbon encapsulation
CN106299344B (en) A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof
CN104377346B (en) Method for preparing modified graphite negative electrode material of sodium ion battery
CN110165210B (en) Preparation method of carbon fluoride anode material with high specific capacity
CN113839058B (en) Carbon-based oxygen reduction reaction catalyst and preparation method thereof
CN103378355B (en) Alkali metal secondary battery and the preparation method of negative electrode active material, negative material, negative pole and negative electrode active material
CN103107307A (en) Water-solution lithium ion battery negative pole material and preparation method thereof
CN117558889A (en) Low-cost composite lithium ion battery anode material, preparation method and application thereof
CN110061236A (en) A kind of preparation method of the three-dimensional porous carbon negative pole material of self-supporting
CN113809286A (en) Metal Organic Framework (MOF) catalyzed growth carbon nanotube coated nickel-tin alloy electrode material and preparation method and application thereof
CN114639809B (en) Composite hard carbon negative electrode material, preparation method and application
CN105417505A (en) Lithium ion battery anode material and preparation method thereof
CN116040605A (en) High-performance hard carbon negative electrode material for high-temperature sodium ion battery and preparation method thereof
CN110510596A (en) A kind of preparation and application of the biomass porous carbon material of nitrogen iron codope
CN114229829B (en) Sodium ion battery anode material based on carbon nano sheet and preparation method and application thereof
CN110034290A (en) A kind of preparation method of sodium-ion battery self-supporting hard carbon cathode material
CN116177520A (en) High-performance hard carbon negative electrode material for low-temperature sodium ion battery and preparation method thereof
CN109728290A (en) A kind of preparation method and applications of transition metal oxide/graphitized intermediate-phase carbosphere composite material
CN115148946A (en) Preparation method of positive pole piece of lithium-sulfur battery and lithium-sulfur battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190705