CN108199003A - A kind of big/mesoporous antimony cathode of three-dimensional, preparation method and applications - Google Patents
A kind of big/mesoporous antimony cathode of three-dimensional, preparation method and applications Download PDFInfo
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- CN108199003A CN108199003A CN201711448321.8A CN201711448321A CN108199003A CN 108199003 A CN108199003 A CN 108199003A CN 201711448321 A CN201711448321 A CN 201711448321A CN 108199003 A CN108199003 A CN 108199003A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of big/mesoporous antimony cathode of three-dimensional, preparation method and applications, and using three-dimensional porous copper as collector, using flexible Zn Sb alloys on the collector, deposition of the Zn Sb alloys on the three-dimensional porous copper is in 0.5~2mg/cm2, then the Zn in the Zn Sb alloys removed by way of heating sublimation to get three-dimensional big/mesoporous antimony cathode.Big/mesoporous antimony of the three-dimensional is used as sodium-ion battery cathode, can greatly improve the capacity fade problem of Sb, height ratio capacity and cyclical stability is obtained, in 100mAg‑1Current density under discharge capacity for the first time can reach 710.6mAhg‑1, after charge and discharge 5 weeks 450mAg is increased in electric current‑1, its charge specific capacity still keeps 451mAhg after 155 weeks‑1, 86% or so of about the 1st week, 94% or so of about the 6th week.The preparation method is simple for process, is produced on a large scale, and low energy consumption, environmental-friendly.
Description
Technical field
The invention belongs to sodium ion battery electrode material technical field, relate generally to a kind of big/mesoporous antimony cathode of three-dimensional,
Preparation method and applications.
Background technology
With the development of electronic equipment, the effect that the lithium ion battery of high-energy density is played the part of in life is increasingly heavier
Will, production cost has increased considerably.Sodium-ion battery because with lithium ion battery have identical ion deinsertion principle,
The cheap prices of raw materials are concerned in terms of extensive energy storage.In numerous anode material of lithium-ion batteries, traditional lithium
Cell negative pole material graphitic carbon does not have embedding sodium capacity, hard carbon material removing sodium current potential (0.1V vs.Na/Na+) close to sodium deposition electricity
Position, battery internal short-circuit caused by dendritic growth so as to cause battery flatulence, bulge, are used up more in large-scale energy storage side
It is hardly imaginable, so finding the problem of suitable anode material of lithium-ion battery is one in the urgent need to address.
In known anode material of lithium-ion battery, the Sb based on alloying reaction has high theoretical specific capacity
(660mAh·g-1) and the advantages that low platform voltage (0.7V vs.S.H.E) and be concerned, but Sb is as sodium-ion battery
Cathode is primarily present following three problems：(1) Sb alloys turn to Na3Its volume expansion is to 390% before, active material after Sb
Material powder of detached problem during volume expansion is serious；(2) low electronic conductivity and ionic conductivity so that active material
The capacity of material is difficult close to its theoretical value；(3) volume expansion causes the SEI films after first charge-discharge unstable, is filled in subsequent
In discharge process, coulombic efficiency is always held at 93%~95%, each time with different degrees of capacity loss.
In view of the above problems, the ameliorative way in currently available technology mainly includes：Alloying improves electric conductivity, constructs
Composite material and regulation and control microscopic appearance slow down volume expansion, improve the chemical property of Sb.The improvement mode of the prior art is deposited more
It is harsh (vacuum melting environment, the voltage of upper kilovolt, high overpotential etc.) in high energy consumption, preparation condition, and change its charge and discharge
The polarization curve and plateau potential of script in electric process.Chan[1]Sb-NiSb-Ni array junctions are prepared Deng with the method for AAO templates
Structure, in 66mAg-1Current density under cycle 300 circle after, capacity still has 391mAhg-1, be equivalent to 59.2% theory
Specific capacity；Zhu etc.[2]The Sb nanofibers prepared with method of electrostatic spinning, in 100mAhg-1Current density it is lower 300 times cycle
350mAhg is still kept afterwards-1。
Bibliography
[1]Chan Woo Lee,Jae-Chan Kim,Sangbaek Park,Hee Jo Song,Dong-Wan Kim,
Highly stable sodium storage in 3-Dgradational Sb–NiSb–Ni heterostructures
[J].Nano Energy,2015,5, 2211-2855.
[2]E.D.Jackson,S.Green,and A.L.Electrospun Sb/C Fibers for a
Stableand Fast Sodium-Ion Battery Anode[J].ACS Nano,2013,5,6378-6386.
Invention content
For the defects in the prior art and insufficient, first purpose of the invention is to provide a kind of big/mesoporous antimony of three-dimensional
Then cathode, the electro-deposition Zn-Sb alloys on three-dimensional porous copper current collector prepare three-dimensional big/Jie by the way of heat treatment
Hole antimony cathode greatly improves the specific surface area of electrode material, and big/meso-hole structure can provide sodium ion quick transmission channel,
Alleviate the volume change in Sb charge and discharge process.
Second object of the present invention is to provide a kind of preparation method of big/mesoporous antimony cathode of three-dimensional, the letter of this method technique
It is single, easy large-scale production.
Third object of the present invention is that big/mesoporous antimony cathode of three-dimensional in the disclosure is used as negative electrode of lithium ion battery
Application, three-dimensional big/mesoporous antimony cathode is in 450mAhg-1Current density under recycle 155 weeks after, still keep 451mAhg-1Reversible capacity, about the 1st week 86% or so, 94% or so of about the 6th week；It is still kept under the current density of 5C
550mAh·g-1Specific capacity.
In order to achieve the above objectives, the technical solution that the present invention takes includes：
First purpose of the present invention is deferred to, a kind of big/mesoporous antimony cathode of three-dimensional using three-dimensional porous copper as collector, is adopted
With flexible Zn-Sb alloys on the collector, deposition of the Zn-Sb alloys on the three-dimensional porous copper exists
0.5~2mg/cm2, then the Zn in the Zn-Sb alloys removed by way of heating sublimation to get three-dimensional big/mesoporous antimony
Cathode.
Optionally, the three-dimensional porous copper is the method using chemical plating in copper sheet surface growing three-dimensional porous membrane layer
It is formed.
Defer to second object of the present invention, a kind of preparation method of big/mesoporous antimony cathode of three-dimensional, with three-dimensional porous copper
For collector, using flexible Zn-Sb alloys on the collector, then the Zn in the Zn-Sb alloys gone
It removes.
Optionally, the preparation method of the three-dimensional porous copper is chemically grown.
Optionally, the antimony source in the flexible Zn-Sb alloys is Sb2O3Or SbCl3, a concentration of 0.01~
0.05mol·L-1；Zinc source is ZnSO4Or ZnCl2, a concentration of 0.1~0.5molL-1；
Optionally, the flexible Zn-Sb alloys include：
Zn-Sb alloy electroplating baths are configured：Contain a concentration of 0.1~0.5molL in Zn-Sb alloy electroplating baths-1ZnSO4, it is dense
It spends for 0.01~0.05molL-1Sb2O3, a concentration of 0.1molL-1Na2SO4, a concentration of 0.18molL-1's
C6H8O7With a concentration of 0.05molL-1H3BO3, adjust Zn-Sb alloy electroplating baths pH=3~4.
Optionally, the deposition voltage that the electrodeposition process uses is 1.4~1.6V.
Optionally, the method for the Zn removals includes：The three-dimensional porous copper that deposition there are Zn-Sb alloys is placed in indifferent gas
400~500 DEG C of heating 4~6h removals Zn in body.
Third object of the present invention is deferred to, big/mesoporous antimony cathode of three-dimensional is as sodium/negative electrode of lithium ion battery
Application.
Alternatively, big/mesoporous antimony cathode of three-dimensional that the preparation method of big/mesoporous antimony cathode of three-dimensional is prepared is made
Application for sodium-ion battery cathode.
Compared with prior art, the beneficial effects of the invention are as follows：
1. three-dimensional big/mesoporous antimony, simple for process, easy scale are prepared using electro-deposition and de- alloyage.
It is 2. three-dimensional by changing Parameter adjustable control in the pore structure of three-dimensional porous copper current collector and control electrodeposition technology
The pore structure of greatly/mesoporous antimony.
3. big/meso-hole structure of three-dimensional big/mesoporous antimony can provide sodium ion quick transmission channel, alleviate Sb charge and discharge
Volume change in journey.
4. three-dimensional big/mesoporous its coulombic efficiency of antimony is after the activation of five circle left and right, coulombic efficiency is maintained at 98~
99%.
5. three-dimensional big/mesoporous antimony cathode is in 450mAhg-1Current density under recycle 155 weeks after, still keep
451mAh·g-1Reversible capacity, about the 1st week 86% or so, 94% or so of about the 6th week；Under the current density of 5C
Still keep 550mAhg-1Specific capacity.
Description of the drawings
Fig. 1 is the high rate performance schematic diagram according to anode material of lithium-ion battery obtained in the embodiment of the present invention 1,
100,200,400,660,1320,3300mAg-1Current density under, embedding sodium specific capacity is respectively 680.5,650,
620,600,550mAhg-1, when current density is reduced to 100mAg-1When its specific discharge capacity remain to reach 680mAhg-1
Left and right；
Fig. 2 is to illustrate according to the long circulating performance of anode material of lithium-ion battery obtained in the embodiment of the present invention 2
Figure, in 450mAg-1Current density under, cycle 155 weeks after its specific capacity still be 457mAhg-1, be equivalent to its 6th
Week completes 96% after activation；
Fig. 3 is to illustrate according to the charging and discharging curve of anode material of lithium-ion battery obtained in the embodiment of the present invention 3
Figure, in 450mAg-1Current density under, cycle removing sodium plateau potential fluctuation very little in its polarization curve after 155 weeks；
Fig. 4 be according to anode material of lithium-ion battery obtained in the embodiment of the present invention 5 SEM photograph (a.2000 times
Lower big/mesoporous antimony SEM photograph of three-dimensional；B.10001 three-dimensional big/mesoporous antimony SEM photograph is descended again；C.500 it is lower three-dimensional big/mesoporous again
Antimony SEM cross-sectional pictures；D.10 three-dimensional big/mesoporous antimony SEM photos under 10,000 times；E.20 three-dimensional big/mesoporous antimony SEM under ten thousand times；
F.50 three-dimensional big/mesoporous antimony SEM photograph under ten thousand times of states)；
Fig. 5 is to be analyzed according to the EDS of big/mesoporous antimony of three-dimensional obtained in the embodiment of the present invention 4,6,7.(a, d, g.)
Electron scanning image, the Elemental redistribution of (b, e, h.) Zn, the Elemental redistribution of (c, f, i.Sb)；
Fig. 6 is big/mesoporous Sb electrodes the sweeping under 100K, 50K, 20K times on three-dimensional porous copper prepared by embodiment 8
Retouch electron microscopic picture；
Fig. 7 is big/mesoporous Sb electrodes the sweeping under 200K, 50K, 20K times on three-dimensional porous copper prepared by embodiment 9
Retouch electron microscopic picture；
Fig. 8 is big/mesoporous Sb electrodes the sweeping under 200K, 50K, 20K times on three-dimensional porous copper prepared by embodiment 10
Retouch electron microscopic picture；
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Specific embodiment
Explanation of nouns：
" three-dimensional porous copper " described in the disclosure refers to that the three-dimensional that the method using chemical plating is grown on copper sheet surface is more
Pore membrane layer.It specifically can be quoted from " CN201710562980.8 ", a kind of entitled " side for preparing the three-dimensional porous Copper thin film of self-supporting
Self-supporting Copper thin film described in method and self-supporting Copper thin film ".
" Zn-Sb alloys " described in the disclosure refers to the Zn-Sb coating materials prepared using constant pressure electro-deposition.
The step of the present invention is as follows:
1) three-dimensional porous copper current collector is prepared；
2) Zn-Sb alloy electroplating baths are configured：Plating solution contains a concentration of 0.1~0.5molL-1ZnSO4·7H2O, it is a concentration of
0.01~0.05molL-1SbCl3, a concentration of 0.1molL-1Na2SO4, a concentration of 0.18molL-1C6H8O7·
H2O, a concentration of 0.05molL-1H3BO3；
3) 240gL is used-1NaOH adjusts pH value to 3~4；
4) using three-dimensional porous copper as substrate, constant pressure electro-deposition obtains Zn-Sb alloys；
5) with acetone, deionized water, alcohol washes removal nail polish after electro-deposition；
6) zinc component is got rid of in heating in Ar gas；
7) under vacuum conditions, 110 DEG C of dry 12h.
Antimony and zinc are deposited on by the method for electro-deposition on three-dimensional porous copper current collector, then heats and goes in Ar gas
Except metallic zinc component, three-dimensional big/mesoporous antimony material is obtained.Big/mesoporous antimony of the three-dimensional is used as sodium-ion battery cathode, can be very big
Improve the capacity fade problem of Sb, obtain height ratio capacity and cyclical stability.The preparation method is simple for process, can scale metaplasia
Production, low energy consumption, environmental-friendly.
The specific implementation of the present invention is only provided with some value citing in the value range of each raw material and process conditions below
Example, it should be noted that the invention is not limited in specific examples below, it should be understood that the value range more than covering, and
And all equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1：
It prepares and uses three-dimensional porous copper as collector；
Zn-Sb plating solutions are configured, plating solution contains a concentration of 0.1molL-1ZnSO4·7H2O, a concentration of 0.01molL-1
Sb2O3, a concentration of 0.1molL-1Na2SO4, a concentration of 0.18molL-1C6H8O7·H2O, it is a concentration of
0.05mol·L-1H3BO3；
Use 240gL-1It is 3 that NaOH, which adjusts pH value,；
Using three-dimensional porous copper as collector, Ag+/ AgCl electrodes be reference electrode, 1.3V potentiostatic electrodepositions；
With deionized water, acetone, washes of absolute alcohol after electro-deposition；
400 DEG C of heating 4h get rid of zinc component in Ar gas；
110 DEG C of heat-treatment of annealing 12h under vacuum conditions obtain three-dimensional big/mesoporous antimony electrode.
In half-cell test, using three-dimensional big/mesoporous antimony as anode, metallic sodium piece is cathode, 1M NaClO4-EC-DEC
For electrolyte, Whatman D/F are diaphragm, are assembled into button cell, charge and discharge are carried out on Land CT2001A charge and discharge instrument
Test.
It will be seen from figure 1 that Sb negative materials prepared by example 1 are in 100mAg-1Current density under reversible specific capacity
For 675mAhg-1, when current density is increased to 3300mAg-1Still there are 550 mAhg when lower-1Reversible specific capacity, quite
In 100mAg-1Under 81%, show superior high rate performance.
Embodiment 2：
The present embodiment step with embodiment 1, unlike, ZnSO in step 24·7H2A concentration of 0.5molL of O-1、
Sb2O3A concentration of 0.05molL-1。
It is tested for the property using assembling mode and test condition same as Example 1.
Figure it is seen that Sb negative materials prepared by embodiment 2 are in 100mAg-1Current density under reversible specific volume
It measures as 525mAhg-1, when current density is increased to 330mAg in the 6th circle-1It will be with 470mAhg when lower-1It is reversible
Specific capacity is equivalent to 100mAg-1Under 89%, be equivalent to the 71% of its theoretical specific capacity, it still has after 200 circle of cycle
470mAh·g-1Reversible specific capacity, be equivalent to its 6th circle 96%, the 89.5% of first lap, show superior follow
Ring stability.
Embodiment 3：
The present embodiment step with embodiment 1, unlike, electro-deposition voltage is 1.5V (VS. Ag in step 5+/AgCl)。
It is tested for the property using assembling mode and test condition same as Example 1.
From figure 3, it can be seen that Sb negative materials prepared by embodiment 3 are in 100mAg-1Current density under discharge for the first time
Specific capacity is about 710mAhg-1, initial charge specific capacity is about 550mAhg-1, the coulombic efficiency for the first time that shows
It is 77.4%, its coulombic efficiency that 99-100% is kept in cyclic process later, its removing sodium electricity after 155 cycles
Position is 0.75V (VS.Na), only improves 0.05V compared with its for the first time removing sodium plateau potential 0.7V (VS.Na), shows excellent
Cyclical stability.
Embodiment 4：
The present embodiment step with embodiment 1, unlike, electro-deposition voltage is 1.6V (VS. Ag in step 5+/AgCl)。
It is observed using Hitachi S4800 cold field emission scanning electron microscope, under 2K, 5K, 500 times of Fig. 4 a, b, c
Three-dimensional porous copper scanning electron microscopic picture, the three-dimensional porous copper product as can be seen from the figure prepared have three-dimensional, interconnected
Interactive hole, pore size is between 2-10um；Scheme d, e, f are big/mesoporous Sb electrodes prepared on three-dimensional porous copper
Scanning electron microscopic picture under 50K, 10K, 20K times, this it appears that it is with 50-100nm or so sizes from figure f
Hole, and be uniformly adhered on three-dimensional porous copper product.
Embodiment 5：
The present embodiment step with embodiment 1, unlike, pH is adjusted to 3.5 in step 3, and heating temperature is in step 7
450 DEG C, time 5h.
Elemental analysis is carried out to embodiment 5 using EMAX energy disperse spectroscopies, the Zn-Sb of electro-deposition is can be seen that from Fig. 5 a, b, c
It is evenly distributed on collector, the electrode material of the pure Sb constituent elements with porous structure can be obtained after removal Zn.
Embodiment 6：
The present embodiment step with embodiment 1, unlike, pH is adjusted to 3.5 in step 3, electro-deposition voltage in step 5
For 1.5V (VS.Ag+/AgCl2), heating temperature is 450 DEG C in step 7, time 5h.
Elemental analysis is carried out to embodiment 6 using EMAX energy disperse spectroscopies, the Zn-Sb of electro-deposition is can be seen that from Fig. 5 d, e, f
It is evenly distributed on collector, the electrode material of the pure Sb constituent elements with porous structure can be obtained after removal Zn.
Embodiment 7：
The present embodiment step with embodiment 1, unlike, pH is adjusted to 3.5 in step 3, electro-deposition voltage in step 5
For 1.6V (VS.Ag+/ AgCl), heating temperature is 450 DEG C in step 7, heating time 5h.
Elemental analysis is carried out to embodiment 7 using EMAX energy disperse spectroscopies, the Zn-Sb of electro-deposition is can be seen that from Fig. 5 g, h, i
It is evenly distributed on collector, the electrode material of the pure Sb constituent elements with porous structure can be obtained after removal Zn.
Embodiment 8：
The present embodiment step with embodiment 1, unlike, pH is adjusted to 4.0 in step 3, and heating temperature is in step 7
500 DEG C, time 6h.
It is observed using Hitachi S4800 cold field emission scanning electron microscope, Fig. 6 is big/Jie on three-dimensional porous copper
Scanning electron microscopic picture of the hole Sb electrodes under 100K, 50K, 20K times, this it appears that it is with a 50-100nm left sides from Fig. 6
The hole of right size, and be uniformly adhered on three-dimensional porous copper product.
Embodiment 9：
The present embodiment step with embodiment 1, unlike, pH is adjusted to 4.0 in step 3, electro-deposition voltage in step 5
For 1.5V (VS.Ag+/ AgCl), heating temperature is 500 DEG C in step 7, time 6h.
It is observed using Hitachi S4800 cold field emission scanning electron microscope, Fig. 7 is big/Jie on three-dimensional porous copper
Scanning electron microscopic picture of the hole Sb electrodes under 200K, 50K, 20K times, this it appears that it is with a 50-150nm left sides from Fig. 7
The hole of right size, and be uniformly adhered on three-dimensional porous copper product.
Embodiment 10：
The present embodiment step with embodiment 1, unlike, pH is adjusted to 4.0 in step 3, electro-deposition voltage in step 5
For 1.6V (VS.Ag+/AgCl2), heating temperature is 500 DEG C in step 7, time 6h.
It is observed using Hitachi S4800 cold field emission scanning electron microscope, Fig. 8 is big/Jie on three-dimensional porous copper
Scanning electron microscopic picture of the hole Sb electrodes under 200K, 50K, 20K times, this it appears that it is with a 50-150nm left sides from Fig. 8
The hole of right size, and be uniformly adhered on three-dimensional porous copper product.
It is described in detail although the present invention has been done and has been cited some optimal embodiments, for the general of this field
Logical technical staff, it is clear that a variety of modifications or alternative solution can be made as specified above, such as：Change plating solution in main salt be
Similar salt；It is similar additive to change the additive in plating solution；It is similar additive to change the complexing agent in plating solution；Change plating
The concentration of each component in liquid；Change the pH value of plating solution；Change the voltage and three electrode Reference systems of plating；Change heating temperature,
Time etc..These alternative solutions and any improvement in the present invention are intended to be included in protection scope of the present invention and open model
Within enclosing.
Claims (10)
1. a kind of big/mesoporous antimony cathode of three-dimensional, which is characterized in that using three-dimensional porous copper as collector, using flexible
Zn-Sb alloys are on the collector, and deposition of the Zn-Sb alloys on the three-dimensional porous copper is in 0.5~2mg/cm2, then
Zn in the Zn-Sb alloys is removed by way of heating sublimation to get three-dimensional big/mesoporous antimony cathode.
2. big/mesoporous antimony cathode of three-dimensional according to claim 1, which is characterized in that the three-dimensional porous copper is uses
The three-dimensional porous film layer that the method for chemical plating is grown on copper sheet surface.
3. a kind of preparation method of big/mesoporous antimony cathode of three-dimensional, which is characterized in that using three-dimensional porous copper as collector, using electricity
Deposition method Zn-Sb alloys are removed on the collector, then by the Zn in the Zn-Sb alloys.
4. the preparation method of big/mesoporous antimony cathode of three-dimensional according to claim 3, which is characterized in that described three-dimensional porous
The preparation method of copper is chemically grown.
5. the preparation method of big/mesoporous antimony cathode of three-dimensional according to claim 3, which is characterized in that the electrodeposition process
It is Sb to deposit the antimony source in Zn-Sb alloys2O3Or SbCl3, a concentration of 0.01~0.05molL-1；Zinc source is ZnSO4Or
ZnCl2, a concentration of 0.1~0.5molL-1。
6. the preparation method of big/mesoporous antimony cathode of three-dimensional according to claim 3, which is characterized in that the electrodeposition process
Deposition Zn-Sb alloys include：
Zn-Sb alloy electroplating baths are configured：Contain a concentration of 0.1~0.5molL in Zn-Sb alloy electroplating baths-1ZnSO4, it is a concentration of
0.01~0.05molL-1Sb2O3, a concentration of 0.1molL-1Na2SO4, a concentration of 0.18molL-1C6H8O7With
A concentration of 0.05molL-1H3BO3, adjust Zn-Sb alloy electroplating baths pH=3~4.
7. the preparation method of big/mesoporous antimony cathode of three-dimensional according to claim 3, which is characterized in that the electrodeposition process
The deposition voltage used is 1.4~1.6V.
8. the preparation method of big/mesoporous antimony cathode of three-dimensional according to claim 3, which is characterized in that the Zn removals
Method includes：The three-dimensional porous copper that deposition there are Zn-Sb alloys is placed in 400~500 DEG C of heating 4~6h removals in inert gas
Zn。
9. application of big/mesoporous antimony cathode of three-dimensional as sodium/negative electrode of lithium ion battery described in claims 1 or 2.
10. the three-dimensional that the preparation method of big/mesoporous antimony cathode of three-dimensional described in claim 3-8 any claims is prepared
Application of the greatly/mesoporous antimony cathode as sodium-ion battery cathode.
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| CN110350146A (en) * | 2019-06-03 | 2019-10-18 | 长安大学 | A kind of porous antimony electrode of modified 3 D, preparation method and application |
| CN111270089A (en) * | 2020-01-20 | 2020-06-12 | 沈阳师范大学 | Mesoporous antimony material and preparation method thereof |
| CN114649508A (en) * | 2022-04-07 | 2022-06-21 | 中国科学院长春应用化学研究所 | Antimony-based integrated electrode and preparation method and application thereof |
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| CN114649508A (en) * | 2022-04-07 | 2022-06-21 | 中国科学院长春应用化学研究所 | Antimony-based integrated electrode and preparation method and application thereof |
| CN114649508B (en) * | 2022-04-07 | 2023-04-07 | 中国科学院长春应用化学研究所 | Antimony-based integrated electrode and preparation method and application thereof |
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