CN108899532A - A kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery and preparation method thereof - Google Patents
A kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery and preparation method thereof Download PDFInfo
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- CN108899532A CN108899532A CN201810438539.3A CN201810438539A CN108899532A CN 108899532 A CN108899532 A CN 108899532A CN 201810438539 A CN201810438539 A CN 201810438539A CN 108899532 A CN108899532 A CN 108899532A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery, the mesoporous micro-pipe shape ZnMn2O4Pore-size distribution be 2~50 nanometers, caliber is 5~25 microns, boss ratio less than 1, draw ratio be greater than 8.The present invention, as template, has synthesized micro-pipe shape ZnMn by using natural cotton fiber2O4, and prepared micro-pipe shape ZnMn2O4Also there is mesoporous characteristic, gained micro-pipe shape ZnMn2O4Have good storage lithium and storage sodium characteristic, have good chemical property as lithium/sode cell negative electrode material, has many advantages, such as to be simple and efficient, is inexpensive.
Description
Technical field
The present invention relates to lithium ion battery and sodium-ion battery technical field, specifically a kind of mesoporous micro-pipe shape ZnMn2O4
Lithium/anode material of lithium-ion battery and preparation method thereof.
Background technique
Zinc manganate (ZnMn2O4) due to its high theoretical capacity, low toxicity and low cost, and become energy and convert and store
The important electrode material in field.But as lithium/sodium electrode negative electrode material, ZnMn2O4Electrode material is due in charge and discharge process
In duplicate ion insertion and extraction and cause its biggish volume change, so that its cycle performance is poor.To solve this problem, respectively
The ZnMn of the different pattern of kind2O4Material is produced.And in the ZnMn of these special appearances2O4In material, it is one-dimensional it is micro-/receive tubulose
The ZnMn of structure2O4Special attention is received, because of the advantages of this structure combines one-dimensional and hollow two kinds of special constructions,
To present good chemical property.As Zhang et al. is prepared for ZnMn using carbon nanotube2O4Nanotube (Longhai
Zhang,Siqi Zhu,Hui Cao,Linrui Hou,Changzhou Yuan.Hierarchical porous ZnMn2O4
Hollow nanotubes with enhanced lithium storage toward lithium~ion batteries
[J] .Chemistry~A European Journal, 2015,21 (30):10771~10777)；Kim et al. is existed using template
ZnMn has been synthesized in titanium substrate2O4Tube array (Jong Guk Kim, Sang Ho Lee, Youngmin Kim, Won Bae
Kim.Fabrication of free~standing ZnMn2O4mesoscale tubular arrays for lithium
~ion anodes with highly reversible lithium storage properties [J] .ACS Applied
Materials&Interfaces,2013,5(21):11321~11328).Although these research resulting materials are in lithium/sode cell
Have good performance in, but their synthetic method it is too cumbersome, it is complicated, need high-cost template etc..
Summary of the invention
The purpose of the invention is to overcome the shortcomings of prior art, a kind of simple process is provided, operation is easy, raw material comes
Lithium/mesoporous ZnMn of sode cell negative electrode material tubulose that source is abundant, low cost and performance are good2O4Preparation method.
The invention is realized in this way：
A kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery, the mesoporous micro-pipe shape ZnMn2O4Pore-size distribution
Be 5~25 microns for 2~50 nanometers, caliber, boss ratio less than 1, draw ratio be greater than 8.
A kind of above-mentioned mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery preparation method, the preparation method
Include the following steps：
（1）Cotton is immersed in the mixed aqueous solution of zinc acetate and manganese acetate, is drawn off carrying out after cotton is impregnated with completely
It is dry；
（2）Cotton after drying is calcined in 400~800 DEG C of temperature to get mesoporous micro-pipe shape ZnMn is arrived2O4Lithium/sodium
Ion battery cathode material.
Preferably, the step（2）For：1~20 parts by weight cotton is immersed the zinc acetate and acetic acid of 80~99 parts by weight
In manganese mixed aqueous solution.
Preferably, step（1）The temperature of the drying is less than 80 DEG C.
Preferably, step（2）The temperature of the calcining is 400~490 DEG C.
Preferably, step（1）The time of the calcining is 1~6 hour.
Preferably, step（2）The zinc acetate and manganese acetate mixed aqueous solution is by 1~20 parts by weight zinc acetate dihydrate
（Zn(CH3COO)2•2H2O）With four water acetic acid manganese（Mn(CH3COO)2•4H2O）The deionization of mixture and 80~99 parts of parts by weight
Water composition.
Preferably, step（2）The zinc acetate dihydrate（Zn(CH3COO)2•2H2O）With four water acetic acid manganese（Mn(CH3COO)2•
4H2O）Mixture is by the zinc acetate dihydrate of 43~50 parts by weight（Zn(CH3COO)2•2H2O）With 50~57 parts by weight, four water vinegar
Sour manganese（Mn(CH3COO)2•4H2O）Composition.
The advantages and positive effects of the present invention：
1, the present invention has synthesized micro-pipe shape ZnM by using natural cotton fiber as templaten2O4, and prepared micro-pipe shape
ZnMn2O4Also there is mesoporous characteristic, gained micro-pipe shape ZnMn2O4Have good storage lithium and storage sodium characteristic, as lithium/sode cell cathode
Material has good chemical property.
2, the present invention is by using 400~800 DEG C of temperature calcinations, and calcining is mild, and burning quality is uniform, and product quality is good.
3, the present invention is formed by using the zinc acetate dihydrate and 50~57 parts by weight, four water acetic acid manganese of 43~50 parts by weight
Immersion mixed aqueous solution, mesoporous micro-pipe shape ZnMn can be improved2O4Lithium/anode material of lithium-ion battery quality.
4, preparation method of the invention and existing preparation ZnMn2O4Preparation method is compared, and is had and is simple and efficient, is inexpensive
The advantages that, there is preferable application value.
5, with document Siqi Zhu, Qiuli Chen, Chao Yang, Yanru Zhang, Linrui Hou,
Gang Pang, Xiangmei He, Xiaogang Zhang, Changzhou Yuan. Biomorphic template-
engaged strategy towards porous zinc manganate micro-belts as a competitive
anode for rechargeable lithium-ion batteries [J]. International Journal of
Hydrogen Energy, 2017, 42(20):14154-14165 is compared, the invention has the advantages that：
A. document above needs first cotton is handled in nitric acid, and the present invention woth no need to the step for, have method letter
Single advantage；
B. it is band-like pattern that document is resulting, there is apparent difference compared with tubulose of the invention.Tubular morphology set is one-dimensional
The advantages of material and hollow pattern, therefore have superior application effect.This is embodied in the specific surface area of the two:Institute of the present invention
The ZnMn obtained2O4The specific surface of material is ~ 48.5 m2 g-1, and the band-like ZnMn of document2O4Specific surface area only have 33 m2 g-1。
C. because of the difference of both the difference of surface area etc. causes chemical property.Such as the resulting ZnMn of the present invention2O4Micro-pipe
In 200 mA g-1First circle discharge capacity is about 1134 mAh g under current density-1, and the band-like ZnMn of document2O4First circle ratio
Capacity is only 1090 mAh g-1。
Detailed description of the invention
The present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is using tubulose ZnMn prepared by the present invention2O4X-ray diffractogram.
Fig. 2 is using ZnMn prepared by the present invention2O4Scanning electron microscope (SEM) photograph, wherein Fig. 2 a be low range scanning electron microscope (SEM) photograph, figure
2b is high magnification scanning electron microscope (SEM) photograph.
Fig. 3 is using the mesoporous ZnMn of tubulose prepared by the present invention2O4Nitrogen adsorption~desorption curve and graph of pore diameter distribution
（Insertion portion in figure）.
Fig. 4 is using the mesoporous ZnMn of tubulose prepared by the present invention2O4As lithium cell cathode material in 200 mA g~1Electric current
Charging and discharging curve under density.
Fig. 5 is using the mesoporous ZnMn of tubulose prepared by the present invention2O4As lithium cell cathode material in 200 mA g~1Electric current
Loop test curve under density.
Fig. 6 is using the mesoporous ZnMn of tubulose prepared by the present invention2O4As sode cell negative electrode material in 100mA g~1Electric current
Charging and discharging curve under density.
Specific embodiment
Below by example, present invention be described in more detail, the present embodiment only illustrate concrete mode of the invention it
One, the usual variations and alternatives that those skilled in the art carry out within the scope of technical solution of the present invention should all be included in of the invention
In protection scope.
Embodiment 1：
Take 0.22 gram of Zn (CH3COO)2·2H2O and 0.4 gram of Mn (CH3COO)2·4H2O is dissolved in 15 grams of deionized waters, then will
0.5 gram of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 60 DEG C of drying.Then suction
Cotton with cobalt nitrate is calcined 3 hours for 700 DEG C in air.Fig. 1 is the XRD diagram of final product, is as can be seen from the figure produced
Object is ZnMn2O4（Card number is No. 24~1133）.From the scanning electron microscope photograph of product（Fig. 2）It can learn ZnMn2O4Powder
Pattern is tubulose（8~15 μm of caliber, draw ratio are averaged 13, boss ratio 1.1）.Fig. 3 is that nitrogen adsorption~desorption of product is bent
Line is mesoporous shape porous mass from product known to curve, and aperture is about 5nm（Insertion figure in Fig. 3）.Its specific surface is 48.5
m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, as a result as shown in figure 4, can send out
First circle specific capacity of the existing electrode material of the invention under the current density of 200 mA/g is 1134.9 mAh/g.In addition to this,
Electrode has preferable cyclical stability, still there is 750.4 mAh/g appearance after 300 circulations under the current density of 200mA/g
Amount output.It can be used as lithium ion battery electrode material use（Fig. 5）.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, as a result as shown in fig. 6, can send out
First circle specific capacity of the existing electrode material of the invention under the current density of 100mA/g is 237.7mAh/g.In addition to this, electrode
There is preferable cyclical stability, still has 102mAh/g volume output after 300 circulations under the current density of 100mA/g.
It can be used as sodium ion battery electrode material use.
Embodiment 2：
Take 0.28 gram of Zn (CH3COO)2·2H2O and 0.38 gram of Mn (CH3COO)2·4H2O is dissolved in 15 grams of deionized waters, then will
1.2 grams of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 50 DEG C of drying.Then suction
Cotton with cobalt nitrate is calcined 1 hour for 800 DEG C in air.It can be seen that product is ZnMn from the XRD diagram of product2O4（Card
Number be No. 24~1133）.ZnMn can be learnt from the scanning electron microscope photograph of product2O4The pattern of powder is tubulose（Caliber 10~
15 μm, draw ratio is average 11, outer internal diameter is than 1.3）.From nitrogen adsorption~desorption curve of product, it is known that product is that mesoporous shape is more
Hole substance, aperture are about 8nm.Its specific surface is 41.5 m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 200 mA/g is 1118.5 mAh/g.In addition to this, electrode has preferably
Cyclical stability still has 765 mAh/g volume outputs after 300 circulations under the current density of 200mA/g.Can be used as lithium from
Sub- battery electrode material uses.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 100 mA/g is 241.7 mAh/g.In addition to this, electrode, which has, preferably follows
Ring stability still has 110 mAh/g volume outputs after 300 circulations under the current density of 100mA/g.It can be used as sodium ion
Battery electrode material uses.
Embodiment 3：
Take 0.18 gram of Zn (CH3COO)2·2H2O and 0.24 gram of Mn (CH3COO)2·4H2O is dissolved in 13 grams of deionized waters, then will
0.6 gram of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 45 DEG C of drying.Then suction
Cotton with cobalt nitrate is calcined 1.5 hours for 590 DEG C in air.It can be seen that product is ZnMn from the XRD diagram of product2O4
（Card number is No. 24~1133）.ZnMn can be learnt from the scanning electron microscope photograph of product2O4The pattern of powder is tubulose（Caliber 8
~10 μm, draw ratio is average 9, outer internal diameter is than 1.14）.From nitrogen adsorption~desorption curve of product, it is known that product is mesoporous shape
Porous mass, aperture are about 6nm.Its specific surface is 43 m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 200 mA/g is 1100.3 mAh/g.In addition to this, electrode has preferably
Cyclical stability still has 777 mAh/g volume outputs after 300 circulations under the current density of 200mA/g.Can be used as lithium from
Sub- battery electrode material uses.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 100 mA/g is 253.1 mAh/g.In addition to this, electrode, which has, preferably follows
Ring stability still has 124 mAh/g volume outputs after 300 circulations under the current density of 100mA/g.It can be used as sodium ion
Battery electrode material uses.
Embodiment 4：
Take 0.32 gram of Zn (CH3COO)2·2H2O and 0.42 gram of Mn (CH3COO)2·4H2O is dissolved in 20 grams of deionized waters, then will
0.8 gram of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 55 DEG C of drying.Then suction
Cotton with cobalt nitrate is calcined 3 hours for 680 DEG C in air.It can be seen that product is ZnMn from the XRD diagram of product2O4（Card
Number be No. 24~1133）.ZnMn can be learnt from the scanning electron microscope photograph of product2O4The pattern of powder is tubulose（Caliber 7~
12 μm, draw ratio is average 10, outer internal diameter is than 1.2）.From nitrogen adsorption~desorption curve of product, it is known that product is that mesoporous shape is more
Hole substance, aperture are about 10nm.Its specific surface is 38.7 m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 200 mA/g is 1109.9 mAh/g.In addition to this, electrode has preferably
Cyclical stability still has 742 mAh/g volume outputs after 300 circulations under the current density of 200mA/g.Can be used as lithium from
Sub- battery electrode material uses.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 100 mA/g is 239.7 mAh/g.In addition to this, electrode, which has, preferably follows
Ring stability still has 133 mAh/g volume outputs after 300 circulations under the current density of 100mA/g.It can be used as sodium ion
Battery electrode material uses.
Embodiment 5：
Take 0.36 gram of Zn (CH3COO)2·2H2O and 0.41 gram of Mn (CH3COO)2·4H2O is dissolved in 10 grams of deionized waters, then will
2 grams of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 70 DEG C of drying.Then absorption
There is the cotton of cobalt nitrate to calcine 2 hours for 750 DEG C in air.It can be seen that product is ZnMn from the XRD diagram of product2O4（Card number
For No. 24~1133）.ZnMn can be learnt from the scanning electron microscope photograph of product2O4The pattern of powder is tubulose（7~16 μ of caliber
M, draw ratio averagely 12, outer internal diameter are than 1.3）.From nitrogen adsorption~desorption curve of product, it is known that product is mesoporous shape porosity
Matter, aperture are about 12nm.Its specific surface is 36.1 m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 200 mA/g is 1130 mAh/g.In addition to this, electrode, which has, preferably follows
Ring stability still has 799 mAh/g volume outputs after 300 circulations under the current density of 200mA/g.It can be used as lithium ion
Battery electrode material uses.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 100 mA/g is 230 mAh/g.In addition to this, electrode has preferable circulation
Stability still has 143 mAh/g volume outputs after 300 circulations under the current density of 100mA/g.It can be used as sodium ion electricity
Pond electrode material uses.
Embodiment 6：
Take 0.32 gram of Zn (CH3COO)2·2H2O and 0.42 gram of Mn (CH3COO)2·4H2O is dissolved in 20 grams of deionized waters, then will
0.8 gram of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 55 DEG C of drying.Then suction
Cotton with cobalt nitrate is calcined 6 hours for 400 DEG C in air.It can be seen that product is ZnMn from the XRD diagram of product2O4（Card
Number be No. 24~1133）.ZnMn can be learnt from the scanning electron microscope photograph of product2O4The pattern of powder is tubulose（Caliber 8~
11 μm, draw ratio is average 10, outer internal diameter is than 1.2）.From nitrogen adsorption~desorption curve of product, it is known that product is that mesoporous shape is more
Hole substance, aperture are about 10nm.Its specific surface is 39.9 m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 200 mA/g is 1109.1 mAh/g.In addition to this, electrode has preferably
Cyclical stability still has 772 mAh/g volume outputs after 300 circulations under the current density of 200mA/g.Can be used as lithium from
Sub- battery electrode material uses.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 100 mA/g is 242.4 mAh/g.In addition to this, electrode, which has, preferably follows
Ring stability still has 135 mAh/g volume outputs after 300 circulations under the current density of 100mA/g.It can be used as sodium ion
Battery electrode material uses.
Embodiment 7：
Take 0.28 gram of Zn (CH3COO)2·2H2O and 0.38 gram of Mn (CH3COO)2·4H2O is dissolved in 15 grams of deionized waters, then will
1.2 grams of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 50 DEG C of drying.Then suction
Cotton with cobalt nitrate is calcined 4 hours for 450 DEG C in air.It can be seen that product is ZnMn from the XRD diagram of product2O4（Card
Number be No. 24~1133）.ZnMn can be learnt from the scanning electron microscope photograph of product2O4The pattern of powder is tubulose（Caliber 12~
14 μm, draw ratio is average 11, outer internal diameter is than 1.2）.From nitrogen adsorption~desorption curve of product, it is known that product is that mesoporous shape is more
Hole substance, aperture are about 7nm.Its specific surface is 40.8 m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 200 mA/g is 1122.1 mAh/g.In addition to this, electrode has preferably
Cyclical stability still has 77 mAh/g volume outputs after 300 circulations under the current density of 200mA/g.Can be used as lithium from
Sub- battery electrode material uses.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 100 mA/g is 248.2 mAh/g.In addition to this, electrode, which has, preferably follows
Ring stability still has 115 mAh/g volume outputs after 300 circulations under the current density of 100mA/g.It can be used as sodium ion
Battery electrode material uses.
Embodiment 8：
Take 0.22 gram of Zn (CH3COO)2·2H2O and 0.4 gram of Mn (CH3COO)2·4H2O is dissolved in 15 grams of deionized waters, then will
0.5 gram of cotton is immersed in above-mentioned solution.It is drawn off after cotton is impregnated with completely, in an oven 60 DEG C of drying.Then suction
Cotton with cobalt nitrate is calcined 5.5 hours for 490 DEG C in air.It can be seen that product is ZnMn from the XRD diagram of product2O4
（Card number is No. 24~1133）.ZnMn can be learnt from the scanning electron microscope photograph of product2O4The pattern of powder is tubulose（Caliber 9
~14 μm, draw ratio is averaged 11, boss ratio 1.3）.It is that mesoporous shape is more from product known to nitrogen adsorption~desorption curve of product
Hole substance, aperture are about 6nm.Its specific surface is 49.9 m2/g。
The ZnMn that will be prepared2O4The half-cell that powder is dressed up carries out storage lithium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 200 mA/g is 1137.1 mAh/g.In addition to this, electrode has preferably
Cyclical stability still has 743.1 mAh/g volume outputs after 300 circulations under the current density of 200mA/g.It can be used as lithium
Ion battery electrode materials use.
The ZnMn being prepared2O4The half-cell that powder is dressed up carries out storage sodium performance test, it is possible to find electrode of the invention
First circle specific capacity of the material under the current density of 100 mA/g is 239.1 mAh/g.In addition to this, electrode, which has, preferably follows
Ring stability still has 104 mAh/g volume outputs after 300 circulations under the current density of 100mA/g.It can be used as sodium ion
Battery electrode material uses.
It is pointed out that the technical concepts and features of above-mentioned preferred embodiment only to illustrate the invention, its object is to
Those skilled in the art can understand the contents of the present invention and implements accordingly, and protection of the invention can not be limited with this
Range.Any equivalent change or modification in accordance with the spirit of the invention should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery, which is characterized in that the mesoporous micro-pipe shape
ZnMn2O4Pore-size distribution be 2~50 nanometers, caliber is 5~25 microns, boss ratio less than 1, draw ratio be greater than 8.
2. a kind of mesoporous micro-pipe shape ZnMn according to claim 12O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, the preparation method includes the following steps：
（1）Cotton is immersed in the mixed aqueous solution of zinc acetate and manganese acetate, is drawn off carrying out after cotton is impregnated with completely
It is dry；
（2）Cotton after drying is calcined in 400~800 DEG C of temperature to get mesoporous micro-pipe shape ZnMn is arrived2O4Lithium/sodium from
Sub- cell negative electrode material.
3. a kind of mesoporous micro-pipe shape ZnMn according to claim 22O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, the step（2）For：The zinc acetate that 1~20 parts by weight cotton immerses 80~99 parts by weight is mixed with manganese acetate
In Heshui solution.
4. a kind of mesoporous micro-pipe shape ZnMn according to claim 22O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, step（1）The temperature of the drying is less than 80 DEG C.
5. a kind of mesoporous micro-pipe shape ZnMn according to claim 22O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, step（2）The temperature of the calcining is 400~490 DEG C.
6. a kind of mesoporous micro-pipe shape ZnMn according to claim 22O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, step（2）The time of the calcining is 1~6 hour.
7. a kind of mesoporous micro-pipe shape ZnMn according to claim 62O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, step（2）The time of the calcining is 3~6 hours.
8. a kind of mesoporous micro-pipe shape ZnMn according to claim 22O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, step（2）The zinc acetate and manganese acetate mixed aqueous solution is by 1~20 parts by weight zinc acetate dihydrate（Zn
(CH3COO)2·2H2O）With four water acetic acid manganese（Mn(CH3COO)2·4H2O）The deionized water of mixture and 80~99 parts of parts by weight
Composition.
9. a kind of mesoporous micro-pipe shape ZnMn according to claim 82O4Lithium/anode material of lithium-ion battery preparation method,
It is characterized in that, step（2）The zinc acetate dihydrate（Zn(CH3COO)2·2H2O）With four water acetic acid manganese（Mn(CH3COO)2·
4H2O）Mixture is by the zinc acetate dihydrate of 43~50 parts by weight（Zn(CH3COO)2·2H2O）With 50~57 parts by weight, four water vinegar
Sour manganese（Mn(CH3COO)2·4H2O）Composition.
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| CN201810438539.3A CN108899532A (en) | 2018-05-09 | 2018-05-09 | A kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery and preparation method thereof |
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| CN115301222B (en) * | 2022-07-11 | 2024-03-15 | 北京工业大学 | Zn-containing alloy 2+ Tubular hollow spinel structure, preparation method and application |
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