CN107946559A - A kind of solvent hot preparation sodium-ion battery anode Sb2Se3The method of/C composite - Google Patents

A kind of solvent hot preparation sodium-ion battery anode Sb2Se3The method of/C composite Download PDF

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CN107946559A
CN107946559A CN201711085746.7A CN201711085746A CN107946559A CN 107946559 A CN107946559 A CN 107946559A CN 201711085746 A CN201711085746 A CN 201711085746A CN 107946559 A CN107946559 A CN 107946559A
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sodium
ion battery
composite
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battery anode
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CN107946559B (en
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曹丽云
郭玲
李嘉胤
黄剑锋
程娅伊
齐慧
席乔
何元元
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Shaanxi University of Science and Technology
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/58—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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

A kind of solvent hot preparation sodium-ion battery anode Sb2Se3The method of/C composite, by SbCl3A1 is obtained in addition absolute ethyl alcohol, carbon source is added A2 is obtained in deionized water, A2 is added solution A is obtained in A1；Se powder is added solution B is obtained in sodium borohydride aqueous solution；Solution B is added dropwise in solution A and obtains mixed liquor C；Mixed liquor C is transferred to polytetrafluoroethyllining lining, is put into homogeneous reaction instrument after 150~200 DEG C are reacted 18~36h, is cooled to room temperature with the furnace, precipitation and separation is washed repeatedly with deionized water and absolute ethyl alcohol, be freeze-dried to obtain sodium-ion battery anode Sb2Se3/ C composite.High-temperature calcination is not required using a step solvent-thermal method in the present invention, and this effectively avoids Sb in calcination process2Se3It is nanocrystalline to grow up, the volume change of bigger is caused, preparation process is simple, and the cycle is short；As sodium-ion battery anode, in 0.1A g‑1Current density under, circulation 50 circle capacity may remain in about 450mAh g‑1, significantly improve cyclical stability.

Description

A kind of solvent hot preparation sodium-ion battery anode Sb2Se3The method of/C composite
Technical field
The invention belongs to anode material of lithium-ion battery preparation field, and in particular to a kind of solvent hot preparation sodium-ion battery Anode Sb2Se3The method of/C composite.
Background technology
The energy is the basis of human social development, and the storage of the energy and conversion have become restriction world economy sustainable development The major issue of exhibition.Develop according to current progress and technology, sodium-ion battery energy storage technology is because have raw material resources It is abundant, it is of low cost, it is widely distributed；High 0.3~the 0.4V of half-cell potential (can utilize the lower electrolyte solvent of decomposition potential And electrolytic salt, the range of choice of electrolyte are wider)；Metastable chemical property, is subject to using the advantage such as safer The concern of numerous researchers, it is believed that the research and development of sodium-ion battery may develop function admirable, the material of safety and stability comes Meet energy demand.The performance of sodium-ion battery is heavily dependent on positive and negative pole material, metallic compound in negative material With high ratio energy, such as antimony base selenides anode material of lithium-ion battery Sb2Se3, a kind of V-VI race with layer structure Compound, as anode material of lithium-ion battery, the Sb of 1mol2Se3Can be with the Na of 12mol+Reaction, makes it have 678mAh·g-1Theoretical capacity.But while bringing high-energy-density with multiple sodium ions generation electrochemical reaction, also make it Itself generate huge volume change.It is anti-with the embedded abjection of sodium ion, high-energy-density anode in charge and discharge process Huge volume change is born again, and easy dusting, peeling, make electrode structure be seriously damaged, so as to cause it to circulate specific volume The rapid decline of amount.
According to the literature, most of research using nanosizing, with inertia it is mutually compound, with carbon material it is compound the methods of reduce Volume change of the high-energy-density anode in charge and discharge process, improves cyclical stability.Wenxi Zhao etc. use " treating different things alike " Method, Sb2Se3 and N doping graphene oxide is compound, and under the current density of 0.1A g-1, discharge capacity is first 1000mA h g-1, capacity still may remain in 560mA h g-1 (Zhao W, Li C M.Mesh- after circulating 50 times structured N-doped graphene@Sb2Se3hybrids as an anode for large capacity sodium-ion batteries.[J].Journal of Colloid&Interface Science,2016,488:356- 364).Xing Qu et al. are compound with reduced graphene by Sb2Se3, under the current density of 1.0A g-1, after circulating 500 times Capacity still may remain in 471mA h g-1 (Ou X, Yang C, Xiong X, et al.A New rGO-Overcoated Sb2Se3Nanorods Anode for Na+Battery:In Situ X‐Ray Diffraction Study on a Live Sodiation/Desodiation Process[J].Advanced Functional Materials,2017.).These reports Road all illustrates the cyclical stability that Sb2Se3 anode material of lithium-ion batteries are obviously improved with carbon material recombination energy, but grinds at present Used carbon source is that graphene this one kind is expensive, material of long preparation period mostly in studying carefully, thus find it is a kind of not only Cheap, the environmentally protective carbon source that can also improve cyclical stability and the preparation method for being adapted to large-scale production are that extremely have Meaning.
The content of the invention
It is an object of the invention to propose a kind of solvent hot preparation sodium-ion battery anode Sb2Se3The side of/C composite Method.Prepared Sb2Se3/ C composite, excellent cyclical stability is shown as anode material of lithium-ion battery.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
1) 1 is pressed：The mass ratio of (1~10) takes SbCl3And carbon source, then by SbCl3Add in absolute ethyl alcohol and stir to complete Dissolving obtains SbCl3Concentration be 0.002moL/L~0.1moL/L clear solution A1, by carbon source addition deionized water stir to Be completely dissolved to obtain the transparent carbon source solution A 2 that carbon source concentration is 0.0023g/mL~0.3422g/mL, by A2 additions A1 stir to It is completely dispersed and is denoted as A；
2) SbCl is pressed3：Se：Sodium borohydride is (0.1~1.5)：(0.15~2.25)：The molar ratio of (0.225~3.375) Sodium borohydride is prepared into the sodium borohydride aqueous solution of 0.015moL/L~0.675moL/L, it is water-soluble that Se powder is added sodium borohydride Stirring obtains clear solution B in liquid；Solution B is quickly added dropwise in solution A under stirring after being dispersed with stirring uniformly and obtains black Mixed liquor C；
3) black mixed liquor C is transferred to polytetrafluoroethyllining lining, be put into homogeneous reaction instrument in 150~200 DEG C of reactions After 18~36h, cool to room temperature with the furnace, precipitation and separation washed repeatedly with deionized water and absolute ethyl alcohol, be freeze-dried sodium from Sub- battery cathode Sb2Se3/ C composite.
Carbon source in the step 1) uses glucose, sucrose, gossypose or beta-cyclodextrin.
Stirring uses magnetic stirring apparatus in the step 1), step 2), and speed of agitator is 500~1000r/min.
The packing ratio that the mixed liquor C of the step 3) is transferred to polytetrafluoroethyllining lining is 30%~80%.
Step 3) the freeze-drying temperature is -40 DEG C, pressure 60Pa.
The sodium-ion battery anode Sb as made of the preparation method of the present invention2Se3/ C composite is carbon-coated nano rod Shape Sb2Se3Structure, bar-shaped Sb2Se3Diameter about 100nm, 5~20nm of carbon layers having thicknesses, and be evenly coated.
Relative to the prior art, the present invention has following beneficial effect：
1) cost is reduced as carbon source using glucose, sucrose, gossypose and beta-cyclodextrin, it is environmentally protective；
2) high-temperature calcination is not required using a step solvent-thermal method, this effectively avoids Sb in calcination process2Se3It is nanocrystalline Grow up, cause the volume change of bigger, preparation process is simple, and the cycle is short；
3) by controlling carbon source addition to prepare the Sb of different carbon layers having thicknesses2Se3/ C composite, and coat equal Even, repeatability is good；
4) Sb prepared using the present invention2Se3/ C composite is as sodium-ion battery anode, in 0.1A g-1Electric current Under density, the circle capacity of circulation 50 may remain in about 450mAh g-1, significantly improve cyclical stability.
The explainable present invention not only meets the requirement of large-scale production in terms of preparation method above, and in performance side Face shows excellent chemical property as sodium-ion battery anode.
Brief description of the drawings
Fig. 1 is Sb prepared by embodiment 12Se3X-ray diffraction (XRD) collection of illustrative plates of electrode material；
Fig. 2 is Sb prepared by embodiment 12Se3Scanning electron microscope (SEM) photo of electrode material；
Fig. 3 is Sb prepared by embodiment 12Se3Transmission electron microscope (TEM) photo of electrode material；
Fig. 4 is Sb prepared by embodiment 12Se3The cycle performance figure of electrode material；Wherein, Cycle number：Circulation time Number；Capacity：Capacity；
Fig. 5 is Sb prepared by embodiment 62Se3Scanning electron microscope (SEM) photo of electrode material；
Fig. 6 is Sb prepared by embodiment 62Se3Transmission electron microscope (TEM) photo of electrode material；
Fig. 7 is Sb prepared by embodiment 62Se3The high rate performance figure of electrode material；Wherein, Cycle number：Circulation time Number；Capacity：Capacity.
Embodiment
This hair is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1：
1) 0.1mmoLSbCl is taken3Add in absolute ethyl alcohol with the magnetic agitation of 500r/min to being completely dissolved to obtain SbCl3 Concentration is the clear solution A1 of 0.002moL/L, by SbCl3It is 1 with carbon source：Carbon source glucose is added deionization by 1 mass ratio Water using the magnetic agitation of 500r/min to being completely dissolved to obtain transparent carbon source solution A 2 of the carbon source concentration as 0.0023g/mL, by A2 Add A1 and stir to being completely dispersed and be denoted as A；
2) sodium borohydride of 0.225mmoL is taken to be prepared into the sodium borohydride aqueous solution of 0.015moL/L, by 0.15mmoL's Se powder adds in sodium borohydride aqueous solution and obtains clear solution B with the magnetic agitation of 500r/min；Under stirring by solution B quickly by It is added dropwise in solution A after being dispersed with stirring uniformly and obtains black mixed liquor C；
3) black mixed liquor C is transferred to polytetrafluoroethyllining lining by 70% packing ratio, be put into homogeneous reaction instrument After 150 DEG C of reaction 36h, room temperature is cooled to the furnace, precipitation and separation, freezing (- 40 are washed repeatedly with deionized water and absolute ethyl alcohol DEG C, 60Pa) dry sodium-ion battery anode Sb2Se3/ C composite.
With Rigaku D/max2000PCX- x ray diffractometer xs analysis sample (Sb2Se3/ C composite granules), find sample with The Sb for the rhombic system that JCPDS numberings are 15-08612Se3Structure is consistent and (Fig. 1) occurs without other miscellaneous peaks；The sample is beautiful The field emission scanning electron microscope (FESEM) of FEI Co. of state S-4800 types is observed, it can be seen that prepared pure phase Sb2Se3Nanocrystalline is club shaped structure, and diameter is about 100nm, and there is coating on surface.(Fig. 2).By sample FEI Co. of the U.S. The Flied emission transmission electron microscope of TecnaiG2F20S-TWIN types is observed, it can be seen that bar-shaped Sb2Se3There is carbon bag on surface Cover, carbon layers having thicknesses about 3nm (Fig. 3).
By sodium-ion battery anode Sb2Se3/ C composite is as active material, by 7:(1:1):(0.5:0.5) matter Ratio is measured by active material and conductive agent (Super-p and electrically conductive graphite), binding agent (hydroxymethyl cellulose CMC and polyacrylic acid PAA) be dissolved in deionized water by grinding, slurry coating, drying, section after as anode in the glove box full of argon gas group Button-shaped sodium-ion battery is dressed up, after shelving 48h, electrochemical property test is carried out using blue electric tester.In 0.1A g-1Electricity Under current density, the circle capacity of circulation 50 may remain in about 400mAh g-1, significantly improve cyclical stability (Fig. 4).
Embodiment 2：
1) 0.3mmoLSbCl is taken3Add in absolute ethyl alcohol with the magnetic agitation of 600r/min to being completely dissolved to obtain SbCl3 Concentration is the clear solution A1 of 0.005moL/L, by SbCl3It is 1 with carbon source：Carbon source sucrose is added deionized water by 3 mass ratio Using the magnetic agitation of 600r/min to being completely dissolved to obtain transparent carbon source solution A 2 of the carbon source concentration as 0.01g/mL, A2 is added A1 is stirred to being completely dispersed and is denoted as A；
2) sodium borohydride of 0.80mmoL is taken to be prepared into the sodium borohydride aqueous solution of 0.052moL/L, by the Se of 0.45mmoL Powder adds in sodium borohydride aqueous solution and obtains clear solution B with the magnetic agitation of 600r/min；Under stirring by solution B quickly dropwise Add in solution A after being dispersed with stirring uniformly and obtain black mixed liquor C；
3) black mixed liquor C is transferred to polytetrafluoroethyllining lining by 80% packing ratio, be put into homogeneous reaction instrument After 160 DEG C of reaction 30h, room temperature is cooled to the furnace, precipitation and separation, freezing (- 40 are washed repeatedly with deionized water and absolute ethyl alcohol DEG C, 60Pa) dry sodium-ion battery anode Sb2Se3/ C composite.
Embodiment 3：
1) 0.7mmoLSbCl is taken3Add in absolute ethyl alcohol with the magnetic agitation of 500r/min to being completely dissolved to obtain SbCl3 Concentration is the clear solution A1 of 0.02moL/L, by SbCl3It is 1 with carbon source：Carbon source gossypose is added deionization by 5 mass ratio Water using the magnetic agitation of 500r/min to being completely dissolved to obtain transparent carbon source solution A 2 of the carbon source concentration as 0.05g/mL, by A2 plus Enter A1 and stir to being completely dispersed to be denoted as A；
2) sodium borohydride of 0.225mmoL is taken to be prepared into the sodium borohydride aqueous solution of 0.143moL/L, by the Se of 1.5mmoL Powder adds in sodium borohydride aqueous solution and obtains clear solution B with the magnetic agitation of 700r/min；Under stirring by solution B quickly dropwise Add in solution A after being dispersed with stirring uniformly and obtain black mixed liquor C；
3) black mixed liquor C is transferred to polytetrafluoroethyllining lining by 60% packing ratio, be put into homogeneous reaction instrument After 170 DEG C of reaction 24h, room temperature is cooled to the furnace, precipitation and separation, freezing (- 40 are washed repeatedly with deionized water and absolute ethyl alcohol DEG C, 60Pa) dry sodium-ion battery anode Sb2Se3/ C composite.
Embodiment 4：
1) 1mmoLSbCl is taken3Add in absolute ethyl alcohol with the magnetic agitation of 700r/min to being completely dissolved to obtain SbCl3It is dense The clear solution A1 for 0.04moL/L is spent, by SbCl3It is 1 with carbon source：Carbon source gossypose is added deionized water by 7 mass ratio Using the magnetic agitation of 700r/min to being completely dissolved to obtain transparent carbon source solution A 2 of the carbon source concentration as 0.1g/mL, A2 is added A1 is stirred to being completely dispersed and is denoted as A；
2) take the sodium borohydride of 2mmoL to be prepared into the sodium borohydride aqueous solution of 0.25moL/L, the Se powder of 1.5mmoL is added Enter in sodium borohydride aqueous solution and clear solution B is obtained with the magnetic agitation of 700r/min；Solution B is quickly added dropwise under stirring Black mixed liquor C is obtained after being dispersed with stirring in solution A uniformly；
3) black mixed liquor C is transferred to polytetrafluoroethyllining lining by 50% packing ratio, be put into homogeneous reaction instrument After 180 DEG C of reaction 20h, room temperature is cooled to the furnace, precipitation and separation, freezing (- 40 are washed repeatedly with deionized water and absolute ethyl alcohol DEG C, 60Pa) dry sodium-ion battery anode Sb2Se3/ C composite.
Embodiment 5：
1) 1.2mmoLSbCl is taken3Add in absolute ethyl alcohol with the magnetic agitation of 600r/min to being completely dissolved to obtain SbCl3 Concentration is the clear solution A1 of 0.08moL/L, by SbCl3It is 1 with carbon source：Carbon source glucose is added deionization by 8 mass ratio Water using the magnetic agitation of 600r/min to being completely dissolved to obtain transparent carbon source solution A 2 of the carbon source concentration as 0.2g/mL, by A2 plus Enter A1 and stir to being completely dispersed to be denoted as A；
2) sodium borohydride of 2.6mmoL is taken to be prepared into the sodium borohydride aqueous solution of 0.386moL/L, by the Se powder of 1.8mmoL Add in sodium borohydride aqueous solution and clear solution B is obtained with the magnetic agitation of 600r/min；Solution B is quickly added dropwise under stirring Enter and obtain black mixed liquor C after being dispersed with stirring in solution A uniformly；
3) black mixed liquor C is transferred to polytetrafluoroethyllining lining by 40% packing ratio, be put into homogeneous reaction instrument After 150 DEG C of reaction 24h, room temperature is cooled to the furnace, precipitation and separation, freezing (- 40 are washed repeatedly with deionized water and absolute ethyl alcohol DEG C, 60Pa) dry sodium-ion battery anode Sb2Se3/ C composite.
Embodiment 6：
1) 1.5mmoLSbCl is taken3Add in absolute ethyl alcohol with the magnetic agitation of 500r/min to being completely dissolved to obtain SbCl3 Concentration is the clear solution A1 of 0.1moL/L, by SbCl3It is 1 with carbon source：10 mass ratio by carbon source beta-cyclodextrin add go from Sub- water using the magnetic agitation of 500r/min to being completely dissolved to obtain transparent carbon source solution A 2 of the carbon source concentration as 0.3422g/mL, will A2, which adds A1 and stirs to being completely dispersed, is denoted as A；
2) sodium borohydride of 3.375mmoL is taken to be prepared into the sodium borohydride aqueous solution of 0.675moL/L, by 2.25mmoL's Se powder adds in sodium borohydride aqueous solution and obtains clear solution B with the magnetic agitation of 600r/min；Under stirring by solution B quickly by It is added dropwise in solution A after being dispersed with stirring uniformly and obtains black mixed liquor C；
3) black mixed liquor C is transferred to polytetrafluoroethyllining lining by 30% packing ratio, be put into homogeneous reaction instrument After 180 DEG C of reaction 18h, room temperature is cooled to the furnace, precipitation and separation, freezing (- 40 are washed repeatedly with deionized water and absolute ethyl alcohol DEG C, 60Pa) dry sodium-ion battery anode Sb2Se3/ C composite.
The sample is observed with the field emission scanning electron microscope (FESEM) of FEI Co. of U.S. S-4800 types, can To find out prepared pure phase Sb2Se3Nanocrystalline is club shaped structure, and diameter is about 100nm, and there is coating (Fig. 5) on surface.Should Sample is observed with the Flied emission transmission electron microscope of FEI Co. of U.S. TecnaiG2F20S-TWIN types, it can be seen that rod Shape Sb2Se3There is carbon coating on surface, and carbon layers having thicknesses about 50nm, is evenly coated (Fig. 6).
By sodium-ion battery anode Sb2Se3/ C composite is as active material, by 7:(1:1):(0.5:0.5) matter Ratio is measured by active material and conductive agent (Super-p and electrically conductive graphite), binding agent (hydroxymethyl cellulose CMC and polyacrylic acid PAA) be dissolved in deionized water by grinding, slurry coating, drying, section after as anode in the glove box full of argon gas group Button-shaped sodium-ion battery is dressed up, after shelving 48h, electrochemical property test is carried out using blue electric tester.In 0.1A g-1Electricity Under current density, the circle capacity of circulation 50 may remain in about 450mAh g-1, significantly improve cyclical stability (Fig. 7).

Claims (5)

  1. A kind of 1. solvent hot preparation sodium-ion battery anode Sb2Se3The method of/C composite, it is characterised in that：
    1) 1 is pressed：The mass ratio of (1~10) takes SbCl3And carbon source, then by SbCl3Add in absolute ethyl alcohol and stir to being completely dissolved Obtain SbCl3Concentration is the clear solution A1 of 0.002moL/L~0.1moL/L, and carbon source addition deionized water is stirred to complete To obtain carbon source concentration be the transparent carbon source solution As 2 of 0.0023g/mL~0.3422g/mL for dissolving, and A2 is added A1 stirs to dividing completely Random notes are A；
    2) SbCl is pressed3：Se：Sodium borohydride is (0.1~1.5)：(0.15~2.25)：The molar ratio of (0.225~3.375) is by boron Sodium hydride is prepared into the sodium borohydride aqueous solution of 0.015moL/L~0.675moL/L, and Se powder is added in sodium borohydride aqueous solution Stirring obtains clear solution B；Solution B is quickly added dropwise in solution A under stirring after being dispersed with stirring uniformly and obtains black mixing Liquid C；
    3) black mixed liquor C is transferred to polytetrafluoroethyllining lining, be put into homogeneous reaction instrument 150~200 DEG C react 18~ After 36h, room temperature is cooled to the furnace, precipitation and separation is washed repeatedly with deionized water and absolute ethyl alcohol, be freeze-dried to obtain sodium ion electricity Pond anode Sb2Se3/ C composite.
  2. 2. solvent hot preparation sodium-ion battery anode Sb according to claim 12Se3The method of/C composite, it is special Sign is：Carbon source in the step 1) uses glucose, sucrose, gossypose or beta-cyclodextrin.
  3. 3. solvent hot preparation sodium-ion battery anode Sb according to claim 12Se3The method of/C composite, it is special Sign is：Stirring uses magnetic stirring apparatus in the step 1), step 2), and speed of agitator is 500~1000r/min.
  4. 4. solvent hot preparation sodium-ion battery anode Sb according to claim 12Se3The method of/C composite, it is special Sign is：The packing ratio that the mixed liquor C of the step 3) is transferred to polytetrafluoroethyllining lining is 30%~80%.
  5. 5. the solvent hot preparation sodium-ion battery anode Sb according to profit requires 12Se3The method of/C composite, its feature It is：Step 3) the freeze-drying temperature is -40 DEG C, pressure 60Pa.
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CN113036139A (en) * 2021-03-10 2021-06-25 陕西科技大学 Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material and preparation method thereof
CN113023706A (en) * 2021-03-10 2021-06-25 陕西科技大学 Carbon-coated antimony selenide/graphene composite material and preparation method and application thereof

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CN106848386A (en) * 2017-01-23 2017-06-13 陕西科技大学 A kind of sodium-ion battery negative pole nest like Sb2Se3The preparation method of electrode material

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TWI725654B (en) * 2019-12-10 2021-04-21 輝能科技股份有限公司 Lithium battery structure and electrode layer thereof
CN113036139A (en) * 2021-03-10 2021-06-25 陕西科技大学 Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material and preparation method thereof
CN113023706A (en) * 2021-03-10 2021-06-25 陕西科技大学 Carbon-coated antimony selenide/graphene composite material and preparation method and application thereof
CN113036139B (en) * 2021-03-10 2022-01-14 陕西科技大学 Se/C/Sb2Se3Double-shell hollow nano rod-shaped sodium ion battery cathode material and preparation method thereof

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