CN108550842A - A kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension and preparation method thereof - Google Patents

A kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension and preparation method thereof Download PDF

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Publication number
CN108550842A
CN108550842A CN201810482843.8A CN201810482843A CN108550842A CN 108550842 A CN108550842 A CN 108550842A CN 201810482843 A CN201810482843 A CN 201810482843A CN 108550842 A CN108550842 A CN 108550842A
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sno
surface area
specific surface
high specific
dimension
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李德军
贺晓东
董雷
冯建民
刘瑞鲜
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Tianjin University
Tianjin Normal University
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Tianjin Normal University
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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 discloses high specific surface area porous shape stannic oxide anode material of lithium-ion batteries of a kind of two dimension and preparation method thereof, using single substance as tin source, tin source dosage controls well, using the mixture of anhydrous ethylenediamine and ethyl alcohol as solvent hot solvent, the moisture of introducing is accurately controlled to adjust the dosage of ethyl alcohol, and moisture directly determines the content of SnO in product.Take full advantage of SnO2Insoluble in dilute HCL, and SnO is dissolved in dilute HCL this chemical characteristic and carrys out pore-creating, to corrode SnO2SnO in ＆SnO composite materials prepares high specific surface area porous two dimension shape SnO to reach2Material.

Description

A kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension and Preparation method
Technical field
The present invention relates to sodium ion battery electrode material fields, and in particular to a kind of high specific surface area porous shape dioxy of two dimension Change tin anode material of lithium-ion battery and preparation method thereof, belongs to technical field of new material preparation.
Background technology
In recent years, with the further development of global industry, the mankind sharply increase demand for energy.At the same time, The caused problem of environmental pollution of industrialization is also further exacerbated by.Seek green, environmentally friendly, reproducible new energy is current section Grind the significant effort direction of personnel.TiS is found from EXXON companies in 19762Deintercalate lithium ions that can be reversible simultaneously develop One lithium rechargeable battery, by 1991, Japanese Sony Corporation released cobalt acid lithium/carbon lithium ion secondary cell of business application Since, by nearly development in 30 years, lithium rechargeable battery has attained full development.But lithium rechargeable battery develops at it It is unstable that it is constantly subjected to its safety factor in the process, energy density can not further increase, and lithium resource reserves are insufficient and are distributed not The puzzlement of the problems such as balanced.Sodium ion secondary battery has no significant difference with lithium rechargeable battery from theory structure, is all It is formed with battery plus-negative plate and different electrolyte.Compared with lithium ion battery, sodium-ion battery has the cost of raw material more Add cheap：Sodium element earth abundance is far above elemental lithium, and the distribution on global equilibrium of sodium element, and cost of winning is cheap equal natural excellent Gesture.In addition, to have many advantages, such as that specific capacity compares lithium rechargeable battery with cycle efficieny high for sodium ion secondary battery, it is more applicable In the application scenarios of extensive energy storage, such as in extensive high-voltage fence energy storage, the base station energy storage of high-speed mobile communications net, big number According to center energy storage, the scenes such as cloud computing center energy storage.
The negative electrode material of commercial li-ion secondary cell is still based on graphitized carbon material at present, graphite-like carbon materials The theoretical lithium storage content of material is 372mAhg-1.But during studying sodium ion secondary battery, Stevens etc. and The researchers such as Fouletier have found respectively, insertion and deintercalation that can be reversible in graphite flake layer relative to lithium ion, ion The sodium ion that radius is 0.98nm is without the smaller lithium ion of image of Buddha interionic distance like that in interlamellar spacing is 0.355nm graphite flake layers Embedded and deintercalation.As the soft charcoal and hard charcoal of non-graphite carbon material, the storage sodium principle and storage lithium principle class of this carbon material in two Seemingly, it is all based on the deintercalation mechanism of ion, the voltage value of the only insertion of lithium/sodium ion is different, and their specific capacity connects Closely.But the irreversible capacity loss of the storage sodium of non-graphite carbon material is larger, cycle performance when high current high magnification is tested It is bad, and the decomposition of battery electrolyte can also influence its embedding sodium performance under high-current test.
In the research for finding suitable sodium ion secondary battery negative material, it has been found that carbon-based material generally existing The problem of efficiency for charge-discharge is low and poor circulation is difficult to overcome.Therefore, find substitute carbon-based material novel anode material at For the task of top priority.The irreversible capacity loss for the first time of transition metal oxide and transient metal sulfide is small, have a safety feature, Many advantages, such as storage sodium specific capacity is high causes the common concern of people.In numerous metal oxides, SnO2Because there have to be suitable Potential plateau, environmental-friendly, and each Sn atomic energy and 3.75 Na atoms combine and form Na15Sn4Alloy cpd, tool There is higher theoretical capacity and is concerned.At the same time, Na is being formed15Sn4The cubical expansivity generated when metal alloy is high Up to 400% or more, huge volume expansion can make SnO2Occur to reunite during battery charging and discharging, be broken, powdered, shadow The structural stability for ringing material, further results in the capacity attenuation of battery.This is to hinder SnO2As sodium ion secondary battery Negative material main difficulty.Two aspects are concentrated mainly on to the research of Sn base negative materials at present：First, to Sn base cathode materials Material carries out nanosizing regulation and control and prepares the Sn based nano-materials of certain pattern by controllable adjustment, to overcome the body of material itself Product expansion；Second, by the way that Sn sills and other materials is compound, Sn sills are supported on other materials such as graphene, carbon On the carriers such as nanotube, to solve its volume expansion.Just because of this, this patent controllably prepares class stone by solvent thermal reaction The SnO of black alkene shape pattern2Nano material, and as sodium ion secondary battery negative material.
Invention content
The invention solves main problem be for SnO in background technology2It is deposited when as anode material of lithium-ion battery Because its reunion, fracture, powdered the shortcomings of cause SnO2The shortcomings that chemical property inactivates.By it is extremely simple, low at Originally, environmental-friendly solvent thermal process, prepares SnO2With SnO compounds, prepared by the rear method using dilute hydrochloric acid corrosion SnO Go out to store up sodium and has excellent performance the porous SnO of two dimension2Nano material.With the high specific surface area porous shape SnO of two dimension2It is negative as sodium-ion battery Pole active material, effectively overcomes SnO2Volume expansion, substantially increase the high specific surface area porous shape SnO of two dimension2Cycle Stability.This method is with SnCl2For the sources Sn, by solvent heat, pickling, washing drying and etc. prepare the excellent of storage sodium performance Sodium ion secondary battery electrode material.
The present invention is achieved by the following technical solutions：
A kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension, is prepared into according to the following steps It arrives：
Step 1: SnO2The preparation of ＆SnO persursor materials：
First stage：Under anaerobic, by ethanol water that anhydrous ethylenediamine and volume fraction are 75-95% according to 100：0 to 90：10 volume ratio carries out being mixed to get solution A, and 1mmol tin is corresponded to according to every 150-200ml anhydrous ethylenediamines Ratio, into solution A, addition tin source obtains reaction solution B；
Second stage：Solution B is carried out under the conditions of 100 DEG C~220 DEG C to hydro-thermal reaction 8~for 24 hours, it is natural after reaction 20-25 degrees Celsius is cooled to, two dimension shape SnO is obtained using high speed centrifugation, absolute ethyl alcohol washing, vacuum drying method2&SnO Composite material；
Step 2: the directional etching removal of SnO materials：
Take the SnO that step 1 obtains2Acid solution is added with uniformly rotten under conditions of stirring ultrasound in ＆SnO composite materials Lose SnO2SnO in ＆SnO composite materials obtains Gao Bibiao using high speed centrifugation, absolute ethyl alcohol washing, vacuum drying method Area porous two dimension shape SnO2Material.
In the above-mentioned technical solutions, in step 1, oxygen free condition is ar gas environment.
In the above-mentioned technical solutions, the tin source is stannous chloride or stannous oxalate.
In the above-mentioned technical solutions, in step 1, hydro-thermal reaction described in second stage is preferably 140 DEG C~200 DEG C.
In the above-mentioned technical solutions, it is 1~6 hour in the time of the corrosion reaction in step 2；The acid is dense Degree is the dilute hydrochloric acid or dust technology of 0.1-0.5mol/L.
Advantages of the present invention is as follows：
Using single substance as tin source, tin source dosage controls well, using the mixture of anhydrous ethylenediamine and ethyl alcohol as solvent heat Solvent accurately controls the moisture of introducing to adjust the dosage of ethyl alcohol, and moisture directly determines SnO in product Content.Take full advantage of SnO2Insoluble in dilute HCL, and SnO is dissolved in dilute HCL this chemical characteristic and carrys out pore-creating, to corrode SnO2&SnO SnO in composite material prepares high specific surface area porous two dimension shape SnO to reach2Material.
Description of the drawings
Fig. 1：The SnO prepared using invention technology2＆SnO composite materials and 2D SnO2XRD spectrum.
Fig. 2：The SnO prepared using invention technology2＆SnO composite materials and 2D SnO2SEM spectrum.
Fig. 3：The SnO prepared using invention technology2＆SnO composite materials and 2D SnO2TEM collection of illustrative plates.
Fig. 4：The 2D SnO prepared using invention technology2Graph of pore diameter distribution.
Fig. 5：The 2D SnO prepared using invention technology2Specific surface area figure.
Fig. 6：The 2D SnO prepared using invention technology2And commercial nano SnO2For the sodium of active material assembling Ion battery cycle performance figure, wherein 1 is SnO of the present invention2Material discharging, 2 be SnO of the present invention2Material charges, and 3 be commercialization SnO2 Material discharging, 4 be commercialization SnO2Material charges.
It for those of ordinary skill in the art, without creative efforts, can be according to above attached Figure obtains other relevant drawings.
Specific implementation mode
In order to enable those skilled in the art to better understand the solution of the present invention, furtherly with reference to specific embodiment Bright technical scheme of the present invention.
Embodiment 1
First, experimental implementation is carried out in the glove box of argon gas atmosphere, and the anhydrous ethylenediamine of a 35ml is added to poly- four In the autoclave of vinyl fluoride liner, solution A is obtained.0.2mmol anhydrous stannous chlorides are added into solution A, are reacted Liquid B.Solution B is transferred in stainless steel cauldron, solvent thermal reaction is carried out for 24 hours in 220 DEG C of baking oven, after reaction certainly Room temperature so is cooled to, high speed centrifugation, absolute ethyl alcohol washing, vacuum drying method is used to obtain two dimension shape SnO later2＆SnO is multiple Condensation material.Take vacuum drying SnO2＆SnO composite materials are added in excess 0.1mol/L dilute hydrochloric acid, stir 1h, are ultrasonically treated 1h uses high speed centrifugation, absolute ethyl alcohol washing, vacuum drying method to obtain high specific surface area porous two dimension shape SnO later2Material Material.
Embodiment 2
First, experimental implementation is carried out in the glove box of argon gas atmosphere, and the anhydrous ethylenediamine of a 35ml is added to poly- four In the autoclave of vinyl fluoride liner, according to anhydrous ethylenediamine：Ethyl alcohol=95：95% ethyl alcohol is added into reaction kettle for 5 amount 1.85ml obtains solution A.0.2mmol anhydrous stannous chlorides are added into solution A, obtain reaction solution B.Solution B is transferred to not It becomes rusty in steel reaction kettle, carries out solvent thermal reaction for 24 hours in 220 DEG C of baking oven, Temperature fall to room temperature, is adopted later after reaction It is washed with high speed centrifugation, absolute ethyl alcohol, vacuum drying method obtains two dimension shape SnO2＆SnO composite materials.It takes vacuum drying SnO2＆SnO composite materials, be added excess 0.25mol/L dilute hydrochloric acid in, stir 1h, be ultrasonically treated 1h, later use at a high speed from The heart, absolute ethyl alcohol washing, vacuum drying method obtain high specific surface area porous two dimension shape SnO2Material.
Embodiment 3
First, experimental implementation is carried out in the glove box of argon gas atmosphere, and the anhydrous ethylenediamine of a 35ml is added to poly- four In the autoclave of vinyl fluoride liner, according to anhydrous ethylenediamine：Ethyl alcohol=90：95% ethyl alcohol is added into reaction kettle for 10 amount 3.89ml obtains solution A.0.2mmol anhydrous stannous chlorides are added into solution A, obtain reaction solution B.Solution B is transferred to not It becomes rusty in steel reaction kettle, carries out solvent thermal reaction for 24 hours in 220 DEG C of baking oven, Temperature fall to room temperature, is adopted later after reaction It is washed with high speed centrifugation, absolute ethyl alcohol, vacuum drying method obtains two dimension shape SnO2＆SnO composite materials.It takes vacuum drying SnO2＆SnO composite materials, be added excess 0.5mol/L dilute hydrochloric acid in, stir 1h, be ultrasonically treated 1h, later using high speed centrifugation, Absolute ethyl alcohol washing, vacuum drying method obtain high specific surface area porous two dimension shape SnO2Material.
Embodiment 4
First, experimental implementation is carried out in the glove box of argon gas atmosphere, and the anhydrous ethylenediamine of a 35ml is added to poly- four In the autoclave of vinyl fluoride liner, according to anhydrous ethylenediamine：Ethyl alcohol=95：95% ethyl alcohol is added into reaction kettle for 5 amount 3.89ml obtains solution A.0.2mmol anhydrous stannous chlorides are added into solution A, obtain reaction solution B.Solution B is transferred to not It becomes rusty in steel reaction kettle, carries out solvent thermal reaction for 24 hours in 180 DEG C of baking oven, Temperature fall to room temperature, is adopted later after reaction It is washed with high speed centrifugation, absolute ethyl alcohol, vacuum drying method obtains two dimension shape SnO2＆SnO composite materials.It takes vacuum drying SnO2＆SnO composite materials, be added excess 0.1mol/L dust technologies in, stir 1h, be ultrasonically treated 1h, later using high speed centrifugation, Absolute ethyl alcohol washing, vacuum drying method obtain high specific surface area porous two dimension shape SnO2Material.
Embodiment 5
First, experimental implementation is carried out in the glove box of argon gas atmosphere, and the anhydrous ethylenediamine of a 35ml is added to poly- four In the autoclave of vinyl fluoride liner, according to anhydrous ethylenediamine：Ethyl alcohol=95：95% ethyl alcohol is added into reaction kettle for 5 amount 3.89ml obtains solution A.0.2mmol anhydrous stannous chlorides are added into solution A, obtain reaction solution B.Solution B is transferred to not It becomes rusty in steel reaction kettle, carries out solvent thermal reaction for 24 hours in 160 DEG C of baking oven, Temperature fall to room temperature, is adopted later after reaction It is washed with high speed centrifugation, absolute ethyl alcohol, vacuum drying method obtains two dimension shape SnO2＆SnO composite materials.It takes vacuum drying SnO2＆SnO composite materials, be added excess 0.25mol/L dust technologies in, stir 1h, be ultrasonically treated 1h, later use at a high speed from The heart, absolute ethyl alcohol washing, vacuum drying method obtain high specific surface area porous two dimension shape SnO2Material.
Embodiment 6
First, experimental implementation is carried out in the glove box of argon gas atmosphere, and the anhydrous ethylenediamine of a 35ml is added to poly- four In the autoclave of vinyl fluoride liner, according to anhydrous ethylenediamine：Ethyl alcohol=95：95% ethyl alcohol is added into reaction kettle for 5 amount 3.89ml obtains solution A.0.2mmol anhydrous stannous chlorides are added into solution A, obtain reaction solution B.Solution B is transferred to not It becomes rusty in steel reaction kettle, carries out solvent thermal reaction for 24 hours in 220 DEG C of baking oven, Temperature fall to room temperature, is adopted later after reaction It is washed with high speed centrifugation, absolute ethyl alcohol, vacuum drying method obtains two dimension shape SnO2＆SnO composite materials.It takes vacuum drying SnO2＆SnO composite materials, be added excess 0.5mol/L dust technologies in, stir 1h, be ultrasonically treated 1h, later using high speed centrifugation, Absolute ethyl alcohol washing, vacuum drying method obtain high specific surface area porous two dimension shape SnO2 materials.
Above-described embodiment is tested, test result is as follows：
As shown in Figure 1, for using the SnO prepared by specific embodiment 2 in figure2＆SnO composite material precursors material and two Tie up porous high-ratio surface SnO2The XRD of material, by XRD diagram as can be seen that the initial sample without pickling and ultrasound is typical SnO2It is formed with SnO diffraction maximums, wherein when 2Theta angles are 26 °, 30 °, 33 °, 38 °, 51 °, 57 °, 63 °, SnO occurs Peak indicates that, there are SnO, the sample after sufficient pickling and ultrasound, above-mentioned diffraction maximum has all completely disappeared, and indicates SnO It fully dissolves, and SnO2There is no react with dilute hydrochloric acid.
Retouched shown in the collection of illustrative plates that electron microscope photographed by Fig. 2, by dilute hydrochloric acid it is qualitative erode SnO after, two-dimentional SnO2 Pattern not destroyed on a large scale, sample still remains intact two-dimentional class graphene-structured.Hereafter high score has been carried out Resolution Flied emission projects electron-microscope scanning, has obtained two-dimentional high specific surface area porous shape SnO2Project Electronic Speculum collection of illustrative plates.
Prepared SnO is clear that by Fig. 32The lattice structure and diffraction ring of material.It under the tem, can be with See SnO2Material is that have ultra-thin nano flake to be constituted, and the thickness of nanometer sheet is in 10nm or less.
As shown in Figure 4, Figure 5, the high specific surface area porous shape SnO of two dimension in embodiment 2 after overpickling2Compare table Area is 200m2/g.The pore-size distribution of synthesized material is concentrated mainly on 3.8nm or so.Up to 200m2The specific surface area of/g With abundant mesoporous presence, the high specific surface area porous shape SnO of two dimension in each embodiment2Specific surface area is 200-240m2/ g, The pore-size distribution of synthesized material is concentrated mainly on 3.5-4.5nm.Illustrate the two-dimentional high-specific surface area prepared using the present invention Cellular SnO2Material has the potentiality as anode material of lithium-ion battery.
In order to the high specific surface area porous shape SnO of two dimension2The performance of material negative material is verified, next, with quotient The Shanghai Aladdin Reagent Company SnO of industry2(specification：50-100nm) the two-dimentional high-specific surface area that synthesizes is more in material and the present invention Poroid SnO2Material tests compared with its property as anode material of lithium-ion battery active material, assembles 3032 buttons Battery is made using sodium piece to electrode, the porous SnO of synthesis2Make cathode, the use of GF/F cellulose membranes is diaphragm, 1M NaPF6 are electricity After solving liquid, charge-discharge test is carried out under the current density of 0.1C, in the voltage charge and discharge section of 2.5-0.01V, in cycle 100 Circle.It is found by Fig. 6, SnO prepared by the present invention2The specific capacity of material is in 280-320mAhg-1, commercial product SnO2Specific volume Amount is in 100-150mAhg-1, illustrate SnO prepared by the present invention2It is shown in the storage sodium performance and cycle performance of material excellent Performance.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal Fall into protection scope of the present invention.

Claims (10)

1. a kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension, it is characterised in that：According to following Step is prepared：
Step 1: SnO2The preparation of ＆SnO persursor materials：
First stage：Under anaerobic, by ethanol water that anhydrous ethylenediamine and volume fraction are 75-95% according to 100： 0 to 90：10 volume ratio carries out being mixed to get solution A, and the ratio of 1mmol tin is corresponded to according to every 150-200ml anhydrous ethylenediamines, Tin source is added into solution A and obtains reaction solution B；
Second stage：Solution B is carried out under the conditions of 100 DEG C~220 DEG C to hydro-thermal reaction 8~for 24 hours, after reaction Temperature fall To 20-25 degrees Celsius, two dimension shape SnO is obtained2＆SnO composite materials；
Step 2: the directional etching removal of SnO materials：
Take the SnO that step 1 obtains2Acid solution is added with homogeneous corrosion under conditions of stirring ultrasound in ＆SnO composite materials SnO2SnO in ＆SnO composite materials obtains high specific surface area porous two dimension shape SnO2Material.
2. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 1, It is characterized in that：In step 1, oxygen free condition is ar gas environment, and hydro-thermal reaction is preferably 140 DEG C~200 described in second stage ℃。
3. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 1, It is characterized in that：The tin source is stannous chloride or stannous oxalate.
4. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 1, It is characterized in that：In step 1, a kind of high specific surface area porous shape stannic oxide sodium of two dimension according to claim 1 from Sub- cell negative electrode material is 1~6 hour in the time of the corrosion reaction in step 2；The acid solution is a concentration of The dilute hydrochloric acid or dust technology of 0.1-0.5mol/L.
5. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 1, It is characterized in that：Specific surface area is 200-240m2/ g, pore size 3.5-4.5nm.
6. a kind of preparation method of the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension, feature exist In：
Step 1: SnO2The preparation of ＆SnO persursor materials：
First stage：Under anaerobic, by ethanol water that anhydrous ethylenediamine and volume fraction are 75-95% according to 100： 0 to 90：10 volume ratio carries out being mixed to get solution A, and the ratio of 1mmol tin is corresponded to according to every 150-200ml anhydrous ethylenediamines, Tin source is added into solution A and obtains reaction solution B；
Second stage：Solution B is carried out under the conditions of 100 DEG C~220 DEG C to hydro-thermal reaction 8~for 24 hours, after reaction Temperature fall To 20-25 degrees Celsius, two dimension shape SnO is obtained2＆SnO composite materials；
Step 2: the directional etching removal of SnO materials：
Take the SnO that step 1 obtains2Acid solution is added with homogeneous corrosion under conditions of stirring ultrasound in ＆SnO composite materials SnO2SnO in ＆SnO composite materials obtains high specific surface area porous two dimension shape SnO2Material.
7. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 6 Preparation method, it is characterised in that：In step 1, oxygen free condition is ar gas environment.
8. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 6 Preparation method, it is characterised in that：The tin source is stannous chloride or stannous oxalate.
9. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 6 Preparation method, it is characterised in that：In step 1, hydro-thermal reaction described in second stage is preferably 140 DEG C~200 DEG C.
10. the high specific surface area porous shape stannic oxide anode material of lithium-ion battery of a kind of two dimension according to claim 6 Preparation method, it is characterised in that：It it is 1~6 hour in the time of the corrosion reaction in step 2；The acid solution is The dilute hydrochloric acid or dust technology of a concentration of 0.1-0.5mol/L.
CN201810482843.8A 2018-05-18 2018-05-18 A kind of high specific surface area porous shape stannic oxide anode material of lithium-ion battery of two dimension and preparation method thereof Pending CN108550842A (en)

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CN109675545A (en) * 2018-12-20 2019-04-26 华中科技大学 A kind of SnO with multi-layer structurexCatalyst, preparation method and application
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CN111313087A (en) * 2019-06-05 2020-06-19 北京纳米能源与***研究所 Electrolyte material, sodium ion solid electrolyte and application thereof, and sodium ion solid battery

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