CN104600249A - Preparation methods of nanometer porous metal and nanometer porous metal and lithium-sulfur battery positive pole material - Google Patents
Preparation methods of nanometer porous metal and nanometer porous metal and lithium-sulfur battery positive pole material Download PDFInfo
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Abstract
The invention provides a preparation method of a nanometer porous metal and a preparation method of a nanometer porous metal and lithium-sulfur battery positive pole material. Soluble SiO2 aerogel as a template is subjected to mild chemical plating to form the nanometer porous metal with a high specific surface area of 50-100cm<2>.g<-1>. The nanometer porous metal has pores of a three-dimensional net structure. The pores comprise micropores, mesopores and macropores. Simple substance sulfur is carried by the pores of the prepared porous metal so that the positive pole material is formed. The positive pole material can effectively improve a lithium-sulfur battery active substance utilization rate, power density and cycling stability.
Description
Technical field
The present invention relates to battery material field, particularly, relate to the preparation method of a kind of nano porous metal preparation method and nano porous metal lithium sulfur battery anode material.
Background technology
In the face of the develop rapidly of new energy technology, particularly along with the fast development of the energy-accumulating power station, electric automobile, intelligent communication etc. of various scale, the task that exploitation has the secondary cell system of more high-energy-density and power density is very urgent.Energy density is high, self discharge is little, operating temperature range is large owing to having for lithium ion battery, memory-less effect and the advantage such as pollution-free, is best one of the secondary cell and optimal electrical source of power of current combination property.But current commercial lithium ion battery is subject to its positive electrode as LiCoO
2, LiMnO
2and LiFePO
4etc. the restriction of relatively low theoretical specific capacity, its highest specific capacity can only reach 100 ~ 300WhKg
-1, be difficult to the requirement meeting high-energy-density and high power density.
The specific capacity of elemental sulfur is up to 1675mAhg
-1, take elemental sulfur as positive active material, lithium metal is that the theoretical energy density of the lithium-sulfur cell of negative pole composition is up to 2600WhKg
-1, be 3 ~ 5 times of traditional lithium ion battery energy density, thus become the focus of current research.But cycle performance is poor, in cyclic process, capacity attenuation is rapidly that current sulphur positive electrode applies the greatest problem run in lithium battery, and reason is that the electronic and ionic insulation of the polysulfide generated in elemental sulfur and course of reaction and polysulfide can be dissolved in organic solvent.Therefore, improve the conductance of sulphur positive electrode, reduction or suppress the dissolving of polysulfide to be the key of dealing with problems.Normally elemental sulfur is loaded at present all kinds of there is loose structure material with carbon element (porous carbon, carbon nano-tube, carbon fiber, Graphene etc.), in conducting high polymers thing (polyaniline, polypyrrole, polyacrylonitrile etc.) material, form composite material, to strengthen the electric conductivity of elemental sulfur and to reduce polysulfide dissolving in the electrolytic solution.And nano porous metal material is except the advantage such as high-specific surface area, high porosity with above-mentioned material, also have the higher conductance that metal material has, nano level metallic framework has stronger suction-operated to elemental sulfur and sulfide simultaneously.Therefore, nano porous metal/elemental sulfur composite material is a kind of high performance lithium sulfur battery anode material.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of nano porous metal, lithium sulfur battery anode material, and this preparation method is with the SiO of solubility
2aeroge is template, utilizes gentle electroless plating method to prepare and has high specific surface area (50 ~ 100cm
2g
-1) nano porous metal, this nano porous metal has the hole of three-dimensional net structure, this hole comprises micropore, mesoporous and macropore, and elemental sulfur loads in the hole of the nano porous metal prepared by positive electrode of the present invention just, lithium-sulfur cell active material utilization, power density and stable circulation performance effectively can be improved.
The present invention's adopted technical scheme that solves the problem is:
A preparation method for nano porous metal material, comprises following step:
(1) module is prepared: by the 3:2:1 mixing by volume of tetraethoxysilane, deionized water and absolute ethyl alcohol, the stannous chloride solution of appropriate 0.1mol/L is first added after stirring, the palladium chloride solution of isopyknic 0.1mol/L is added again after stirring, in 60-80 DEG C of water bath with thermostatic control, leave standstill a period of time after stirring, obtain the silica hydrogel template of even sensitization-activation;
(2) pre-soaking: silica hydrogel template step (1) prepared after preparation metal target chemical plating fluid is placed in metal target chemical plating fluid pre-soaking 1-3 days in ambient temperatare;
(3) chemical plating preparation process: the template after step (2) pre-soaking is placed in circulating flowing device, implements chemical plating under 40-60 DEG C of condition, plating time is 15-20 days, obtains metal/silica hydrogel compound;
(4) the laggard row exchange of solvent of metal/silica hydrogel compound washed with de-ionized water step (3) obtained also obtains metal/silicon dioxide silica aerogel composite material after carrying out supercritical drying;
(5) module is gone: the nano porous metal material obtaining having three-dimensional network-like structure after metal/silicon dioxide silica aerogel composite material is removed silicon dioxide module.
Further, described metal target is copper, and corresponding chemical plating fluid is
Further, described metal target is nickel, and corresponding chemical plating fluid is
Further, described metal target is silver, and corresponding chemical plating fluid is
Further, described metal target is iron, and corresponding chemical plating fluid is
A preparation method for nano porous metal, lithium sulfur battery anode material, comprises the following steps:
A nano porous metal according to any one of claim 1 and 5 mixes according to weight ratio 1:0.2 ~ 0.8 with elemental sulfur by ();
B elemental sulfur/the nano porous metal mixed in step a is placed in tube furnace by (), under inert gas Ar gas shielded, with 1 DEG C of min
-1heating rate be warming up to 155 DEG C, 155 DEG C insulation 2 ~ 5h, obtain elemental sulfur/nano porous metal composite material;
C elemental sulfur/nano porous metal composite material that () will obtain in step b, add conductive agent and bonding agent again, be uniformly mixed, obtain mixture, the mass ratio of wherein elemental sulfur/nano porous metal composite material, conductive agent and bonding agent is 1:0.8 ~ 0.9:0.8 ~ 0.9;
Add appropriate 1-METHYLPYRROLIDONE in d mixture that () obtains to step c, stir, the slurry blade coating being modulated into moderate concentration, in Al paper tinsel collection liquid surface, namely obtains elemental sulfur/nano porous metal composite material positive plate after vacuumize.
Further, the conductive agent of described step c is acetylene black or super carbon.
Further, the bonding agent of described step c is Kynoar or polytetrafluoroethylene.
To sum up, the invention has the beneficial effects as follows:
1, nano porous metal is a kind of material with three-dimensional network-like structure, there is the advantage that specific area is large, porosity is high, this elemental sulfur that can hold more amount is in its pore structure, ensure that the content of active material and the high power capacity of battery, the initial charge specific capacity of battery is up to 1563mAhg
-1, first discharge specific capacity is up to 1425mAhg
-1, after 50 circulations, capability retention is 80.3%;
2, by the pore structure of adjusting template, the porosity of the adjustable nano porous metal prepared and specific area, therefore can prepare the lithium-sulfur cell with different specific energy and specific power, adapts to the demand of different application;
3, metal has than material with carbon element and the better mechanical performance of macromolecular material, and this makes the nano porous metal/elemental sulfur combination electrode prepared more easily be processed into different shapes, to adapt to the requirement in different application field.
Accompanying drawing explanation
Fig. 1 is the three-dimensional network loose structure figure of nano porous copper;
Fig. 2 is the N of nano porous copper
2suction-desorption curve;
When Fig. 3 is 0.2C for testing multiplying power, test 50 circle cycle performances.
Embodiment
Below in conjunction with embodiment and accompanying drawing, to the detailed description further of the present invention's do, but embodiments of the present invention are not limited thereto.
Prepared by embodiment 1 nanoporous copper product
First the SiO of even sensitization-activation is prepared
2aeroge template, by tetraethoxysilane, absolute ethyl alcohol and deionized water by volume for the proportional quantities of 3:2:1 is taken in beaker, first adds appropriate 0.1molL after stirring
-1snCl
2solution is (with the S nCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with SnCl
2solution), add the 0.1molL of equivalent after stirring
-1pdCl
2solution is (with the PdCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with PdCl
2solution), be transferred in colorimetric cylinder by solution after stirring and seal, the water bath with thermostatic control being placed in 80 DEG C leaves standstill 3 days, namely prepares the SiO of even sensitization-activation
2hydrogel.Next prepares chemical bronze plating liquid, consisting of of chemical bronze plating liquid: natrium citricum 20gL
-1, boric acid 30gL
-1, copper sulphate 5gL
-1, inferior sodium phosphate 30gL
-1.By the SiO of even sensitization-activation prepared
2aeroge immerses in the chemical bronze plating liquid prepared, flood under room temperature after 1 ~ 2 day, chemical plating is implemented in the water bath with thermostatic control of 60 DEG C, chemical plating duration is 20 days, obtain copper-hydrogel composite material, then this composite material is spent deionized water, until non-metallic ion in cleaning fluid, carry out exchange of solvent with acetone until record with micro-water analyzer the content exchanging moisture in rear acetone to complete exchange of solvent lower than during 3000ppm, then this composite material is put into CO
2dry in supercritical drying instrument, reaction condition is 40 DEG C, and 10MPa obtains copper-aerogel composite, then copper-aerogel composite is put into 0.1molL
-1hydrofluoric acid solution in soak remove out SiO
2aeroge template, the nanoporous copper product of the bulk of system.Obtained nano porous copper has three-dimensional network loose structure (Fig. 1).Fig. 2 is the N of nano porous copper
2suction-desorption curve, can find out that there is obvious magnetic hysteresis loop, according to the classification of IUPAC (IUPAC), this curve has the adsorption isotherm line features of IV type, adsorption configuration is close to H3 type, this illustrates that obtained nano porous copper belongs to mesoporous and poromerics, and its specific area is 90.56m
2g
-1, average pore size is 7.3nm.
Prepared by embodiment 2 nanoporous nickel material
First the SiO of even sensitization-activation is prepared
2aeroge template, by tetraethoxysilane, absolute ethyl alcohol and deionized water by volume for the proportional quantities of 3:2:1 is taken in beaker, first adds appropriate 0.1molL after stirring
-1snCl
2solution is (with the S nCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with SnCl
2solution), add the 0.1molL of equivalent after stirring
-1pdCl
2solution is (with the PdCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with PdCl
2solution) stir after solution be transferred in colorimetric cylinder seal, the water bath with thermostatic control being placed in 80 DEG C leaves standstill 3 days, namely prepares the SiO of even sensitization-activation
2hydrogel.Next prepares chemical nickel-plating liquid, consisting of of chemical nickel-plating liquid: natrium citricum 10gL
-1, sodium acetate 5gL
-1, nickelous sulfate 30gL
-1, softex kw 2gL
-1.By the SiO of even sensitization-activation prepared
2aeroge immerses in the chemical nickel-plating liquid prepared, flood under room temperature after 1 ~ 2 day, chemical plating is implemented in the water bath with thermostatic control of 40 DEG C, chemical plating duration is 20 days, obtain nickel-hydrogel composite material, then this composite material is spent deionized water, until non-metallic ion in cleaning fluid, carry out exchange of solvent with acetone until record with micro-water analyzer the content exchanging moisture in rear acetone to complete exchange of solvent lower than during 3000ppm, then this composite material is put into CO
2dry in supercritical drying instrument, reaction condition is 40 DEG C, and 10MPa obtains copper-aerogel composite, then copper-aerogel composite is put into 0.1molL
-1hydrofluoric acid solution in soak remove SiO
2aeroge template, the nanoporous nickel material of the bulk of system.Its specific area is 55.821m
2g
-1, average pore size is 8.61nm.
Prepared by embodiment 3 nanoporous ag material
First the SiO of even sensitization-activation is prepared
2aeroge template, by tetraethoxysilane, absolute ethyl alcohol and deionized water by volume for the proportional quantities of 3:2:1 is taken in beaker, first adds appropriate 0.1molL after stirring
-1snCl
2solution (first adds appropriate 0.1molL after stirring
-1snCl
2solution is (with the S nCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with SnCl
2solution), add the 0.1molL of equivalent after stirring
-1pdCl
2solution is (with the PdCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with PdCl
2solution), be transferred in colorimetric cylinder by solution after stirring and seal, the water bath with thermostatic control being placed in 80 DEG C leaves standstill 3 days, namely prepares the SiO of even sensitization-activation
2hydrogel.Next prepares chemical plating liquid, consisting of of chemical plating liquid: silver nitrate 4gL
-1, absolute ethyl alcohol 100mlL
-1, NaOH 4gL
-1, ammoniacal liquor (mass percent is 28wt%) 100mlL
-1, KI 0.8gL
-1.By the SiO of even sensitization-activation prepared
2aeroge immerses in the chemical plating liquid prepared, flood under room temperature after 1 ~ 2 day, chemical plating is implemented in the water bath with thermostatic control of 60 DEG C, chemical plating duration is 20 days, obtain silver-hydrogel composite material, then this composite material is spent deionized water, until non-metallic ion in cleaning fluid, carry out exchange of solvent with acetone until record with micro-water analyzer the content exchanging moisture in rear acetone to complete exchange of solvent lower than during 3000ppm, then this composite material is put into CO
2dry in supercritical drying instrument, reaction condition is 40 DEG C, and 10MPa obtains silver-aerogel composite, then silver-aerogel composite is put into 0.1molL
-1hydrofluoric acid solution in soak remove out SiO
2aeroge template, pulverous nanoporous ag material of system.The specific area of obtained nano-porous silver is 35.391m
2g
-1, average pore size is 7.546nm.
Prepared by embodiment 4 nanoporous iron material
First the SiO of even sensitization-activation is prepared
2aeroge template, by tetraethoxysilane, absolute ethyl alcohol and deionized water by volume for the proportional quantities of 3:2:1 is taken in beaker, first adds appropriate 0.1molL after stirring
-1snCl
2solution is (with the S nCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with SnCl
2solution), add the 0.1molL of equivalent after stirring
-1pdCl
2solution is (with the PdCl that 30wt% dissolving with hydrochloric acid is appropriate
2be mixed with PdCl
2solution), be transferred in colorimetric cylinder by solution after stirring and seal, the water bath with thermostatic control being placed in 80 DEG C leaves standstill 3 days, namely prepares the SiO of even sensitization-activation
2hydrogel.Prepare chemical iron plating liquid, consisting of of chemical plating iron liquid: iron ammonium sulfate 15gL
-1, sodium borohydride 50gL
-1, natrium citricum 10gL
-1, lactic acid 10gL
-1, propionic acid 2gL
-1, pH value is adjusted to 8 ~ 9.By the SiO of even sensitization-activation prepared
2aeroge immerses in the chemical plating iron liquid prepared, flood under room temperature after 2 days, chemical plating is implemented in the water bath with thermostatic control of 60 DEG C, chemical plating duration is 20 days, obtain iron-hydrogel composite material, then this composite material is spent deionized water, until non-metallic ion in cleaning fluid, carry out exchange of solvent with acetone until record with micro-water analyzer the content exchanging moisture in rear acetone to complete exchange of solvent lower than during 3000ppm, then this composite material is put into CO
2dry in supercritical drying instrument, reaction condition is 40 DEG C, and 10MPa obtains iron-aerogel composite, then iron-aerogel composite is put into 0.1molL
-1hydrofluoric acid solution in soak remove out SiO
2aeroge template, pulverous nanoporous iron material of system.Its specific area is 50.765m
2g
-1, average pore size is 9.53nm.
The preparation of embodiment 5 lithium-sulfur cell elemental sulfur/nano porous copper composite positive pole
Elemental sulfur/nano porous copper composite positive pole prepared by the nanoporous copper product of Example 1.
Nano porous copper is mixed according to weight ratio 1:0.4 with elemental sulfur, the mixture of elemental sulfur and nano porous copper is sealed in ampere bottle, is then placed in the tube furnace of temperature programmed control, under inert gas Ar gas shielded, with 1 DEG C of min
-1heating rate be warming up to 155 DEG C, 155 DEG C insulation 2 ~ 5h, obtain elemental sulfur/nanoporous carbon/carbon-copper composite material.
In mass ratio for positive electrode: super carbon: the Kynoar that Kynoar=1:0.9:0.9 takes the elemental sulfur/nano porous copper composite positive pole of 1g, the super carbon of 0.9g and 0.9g mixes, add appropriate 1-METHYLPYRROLIDONE, after grinding evenly, blade coating is in Al paper tinsel collection liquid surface, coating layer thickness is 200um, namely obtains elemental sulfur/nano porous copper anode composite sheet after vacuumize.
Above-mentioned elemental sulfur/nano porous copper anode composite sheet, PE/PP/PE barrier film and lithium sheet negative plate are assembled into 2032 button cells, inject electrolyte (1M LiTFSI/DOL:DME (1:1)), seal thick rear standing 12h for electrochemical property test, probe temperature is room temperature, test multiplying power is 0.2C, and test voltage scope is 1.0 ~ 3.0V.The calculating of the specific capacity described in the present invention is that benchmark obtains by the content of sulphur in positive electrode, and test result is as shown in table 1.
The preparation of embodiment 6 lithium-sulfur cell elemental sulfur/nanoporous nickel composite positive pole
The nanoporous nickel material of Example 2 prepares elemental sulfur/nanoporous nickel composite positive pole
Nanoporous nickel is mixed according to weight ratio 1:0.6 with elemental sulfur, the mixture of elemental sulfur and nanoporous nickel is sealed in ampere bottle, is then placed in the tube furnace of temperature programmed control, under inert gas Ar gas shielded, with 5 DEG C of min
-1heating rate be warming up to 155 DEG C, 155 DEG C insulation 2 ~ 5h, obtain elemental sulfur/nanoporous nickel composite material.
In mass ratio for positive electrode: super carbon: the Kynoar that Kynoar=1:0.8:0.8 takes the elemental sulfur/nanoporous nickel composite positive pole of 1g, the super carbon of 0.8g and 0.8g mixes, add appropriate 1-METHYLPYRROLIDONE, after grinding evenly, blade coating is in Al paper tinsel collection liquid surface, coating layer thickness is 200um, namely obtains elemental sulfur/nanoporous nickel anode composite sheet after vacuumize.
Above-mentioned elemental sulfur/nanoporous nickel anode composite sheet, PE/PP/PE barrier film and lithium sheet negative plate is assembled into 2032 button cells, inject electrolyte (1M LiTFSI/DOL:DME (1:1)), seal thick rear standing 12h for electrochemical property test, probe temperature is room temperature, test multiplying power is 0.2C, and test voltage scope is 1.0 ~ 3.0V.When Fig. 3 is 0.2C for testing multiplying power, test 50 circle cycle performance figure.The calculating of the specific capacity described in the present invention is that benchmark obtains by the content of sulphur in positive electrode, and test result is as shown in table 1.
The preparation of embodiment 7 lithium-sulfur cell elemental sulfur/nanoporous nickel composite positive pole
The nanoporous nickel material of Example 2 prepares elemental sulfur/nanoporous nickel composite positive pole
Nanoporous nickel is mixed according to weight ratio 1:0.2 with elemental sulfur, the mixture of elemental sulfur and nanoporous nickel is sealed in ampere bottle, is then placed in the tube furnace of temperature programmed control, under inert gas Ar gas shielded, with 1 DEG C of min
-1heating rate be warming up to 150 DEG C, 150 DEG C insulation 2 ~ 5h, obtain elemental sulfur/nanoporous nickel composite material.
In mass ratio for positive electrode: super carbon: the Kynoar that Kynoar=1:0.9:0.9 takes the elemental sulfur/nanoporous nickel composite positive pole of 1g, the super carbon of 0.9g and 0.9g mixes, add appropriate 1-METHYLPYRROLIDONE, after grinding evenly, blade coating is in Al paper tinsel collection liquid surface, coating layer thickness is 200um, namely obtains elemental sulfur/nanoporous nickel anode composite sheet after vacuumize.
Above-mentioned elemental sulfur/nanoporous nickel anode composite sheet, PE/PP/PE barrier film and lithium sheet negative plate is assembled into 2032 button cells, inject electrolyte (1M LiTFSI/DOL:DME (1:1)), seal thick rear standing 12h for electrochemical property test, probe temperature is room temperature, test multiplying power is 0.2C, and test voltage scope is 1.0 ~ 3.0V.When Fig. 3 is 0.2C for testing multiplying power, test 50 circle cycle performance figure.The calculating of the specific capacity described in the present invention is that benchmark obtains by the content of sulphur in positive electrode, and test result is as shown in table 1.
The preparation of embodiment 8 lithium-sulfur cell elemental sulfur/nano-porous silver composite positive pole
The nanoporous ag material of Example 3 prepares elemental sulfur/nano-porous silver composite positive pole
Nano-porous silver is mixed according to weight ratio 1:0.7 with elemental sulfur, the mixture of elemental sulfur and nano-porous silver is sealed in ampere bottle, is then placed in the tube furnace of temperature programmed control, under inert gas Ar gas shielded, with 1 DEG C of min
-1heating rate be warming up to 155 DEG C, 155 DEG C insulation 2 ~ 5h, obtain elemental sulfur/nanoporous silver composite material.
In mass ratio for positive electrode: super carbon: the Kynoar that Kynoar=1:0.8:0.8 takes the elemental sulfur/nano-porous silver composite positive pole of 1g, the super carbon of 0.8g and 0.8g mixes, add appropriate 1-METHYLPYRROLIDONE, after grinding evenly, blade coating is in Al paper tinsel collection liquid surface, coating layer thickness is 200um, namely obtains elemental sulfur/nano-porous silver anode composite sheet after vacuumize.
Above-mentioned elemental sulfur/nano-porous silver anode composite sheet, PE/PP/PE barrier film and lithium sheet negative plate are assembled into 2032 button cells, inject electrolyte (1M LiTFSI/DOL:DME (1:1)), seal thick rear standing 12h for electrochemical property test, probe temperature is room temperature, test multiplying power is 0.2C, and test voltage scope is 1.0 ~ 3.0V.The calculating of the specific capacity described in the present invention is that benchmark obtains by the content of sulphur in positive electrode, and test result is as shown in table 1.
The preparation of embodiment 9 lithium-sulfur cell elemental sulfur/nanoporous iron composite positive pole
The nanoporous iron material of Example 4 prepares elemental sulfur/nanoporous iron composite positive pole
Nanoporous iron is mixed according to weight ratio 1:0.8 with elemental sulfur, the mixture of elemental sulfur and nanoporous iron is sealed in ampere bottle, is then placed in the tube furnace of temperature programmed control, under inert gas Ar gas shielded, with 1 DEG C of min
-1heating rate be warming up to 155 DEG C, 155 DEG C insulation 2 ~ 5h, obtain elemental sulfur/nanoporous iron composite material.
In mass ratio for positive electrode: super carbon: the Kynoar that Kynoar=1:0.85:0.85 takes the elemental sulfur/nanoporous iron composite positive pole of 1g, the super carbon of 0.85g and 0.85g mixes, add appropriate 1-METHYLPYRROLIDONE, after grinding evenly, blade coating is in Al paper tinsel collection liquid surface, coating layer thickness is 200um, namely obtains elemental sulfur/nanoporous iron anode composite sheet after vacuumize.
Above-mentioned elemental sulfur/nanoporous iron anode composite sheet, PE/PP/PE barrier film and lithium sheet negative plate is assembled into 2032 button cells, inject electrolyte (1M LiTFSI/DOL:DME (1:1)), seal thick rear standing 12h for electrochemical property test, probe temperature is room temperature, test multiplying power is 0.2C, and test voltage scope is 1.0 ~ 3.0V.The calculating of the specific capacity described in the present invention is that benchmark obtains by the content of sulphur in positive electrode, and test result is as shown in table 1.
The charge-discharge performance of table 1 elemental sulfur nano porous metal
As can be seen from Table 1, the mean first charge specific capacity of nano porous metal lithium sulfur battery anode material that prepared by the present invention is 1462.2mAhg
-1, mean first specific discharge capacity is 1297mAhg
-1, initial charge specific capacity is up to 1563mAhg
-1, first discharge specific capacity is up to 1425mAhg
-1, after 50 circulations, capability retention is 80.3%, ensure that high power capacity and the cyclical stability of battery.
As mentioned above, the present invention can be realized preferably.
Claims (9)
1. the preparation method of nano porous metal material, is characterized in that, comprises following step:
Preparation module: by the 3:2:1 mixing by volume of tetraethoxysilane, deionized water and absolute ethyl alcohol, the stannous chloride solution of appropriate 0.1mol/L is first added after stirring, the palladium chloride solution of isopyknic 0.1mol/L with stannous chloride solution is added again after stirring, in 60-80 DEG C of water bath with thermostatic control, leave standstill a period of time after stirring, obtain the silica hydrogel template of even sensitization-activation;
Pre-soaking: silica hydrogel template step (1) prepared after preparation metal target chemical plating fluid is placed in metal target chemical plating fluid pre-soaking 1-3 days in ambient temperatare;
Chemical plating preparation process: the template after step (2) pre-soaking is placed in circulating flowing device, implements chemical plating under 40-60 DEG C of condition, plating time is 15-20 days, obtains metal/silica hydrogel compound; The laggard row exchange of solvent of metal/silica hydrogel compound washed with de-ionized water step (3) obtained also obtains metal/silicon dioxide silica aerogel composite material after carrying out supercritical drying;
Go module: the nano porous metal material obtaining having three-dimensional network-like structure after metal/silicon dioxide silica aerogel composite material is removed silicon dioxide module.
2. the preparation method of nano porous metal material according to claim 1, is characterized in that, described metal target is one in copper, nickel, silver or iron.
3. the preparation method of nano porous metal material according to claim 1, is characterized in that, described metal target is copper, and corresponding chemical plating fluid is
4. the preparation method of nano porous metal material according to claim 1, is characterized in that, described metal target is nickel, and corresponding chemical plating fluid is
5. the preparation method of nano porous metal material according to claim 1, is characterized in that, described metal target is silver, and corresponding chemical plating fluid is
6. the preparation method of nano porous metal material according to claim 1, is characterized in that, described metal target is iron, and corresponding chemical plating fluid is
7. the preparation method of nano porous metal, lithium sulfur battery anode material, is characterized in that, comprises the following steps:
A nano porous metal according to any one of claim 1 and 5 mixes according to weight ratio 1:0.2 ~ 0.8 with elemental sulfur by ();
B elemental sulfur/the nano porous metal mixed in step a is placed in tube furnace by (), under inert gas Ar gas shielded, with 1 DEG C of min
-1heating rate be warming up to 155 DEG C, 155 DEG C insulation 2 ~ 5h, obtain elemental sulfur/nano porous metal composite material;
C elemental sulfur/nano porous metal composite material that () will obtain in step b, add conductive agent and bonding agent again, be uniformly mixed, obtain mixture, the mass ratio of wherein elemental sulfur/nano porous metal composite material, conductive agent and bonding agent is 1:0.8 ~ 0.9:0.8 ~ 0.9;
Add appropriate 1-METHYLPYRROLIDONE in d mixture that () obtains to step c, stir, the slurry blade coating being modulated into moderate concentration, in Al paper tinsel collection liquid surface, namely obtains elemental sulfur/nano porous metal composite material positive plate after vacuumize.
8. the preparation method of nano porous metal according to claim 1, lithium sulfur battery anode material, is characterized in that, the conductive agent of described step c is acetylene black or super carbon.
9. the preparation method of nano porous metal according to claim 1, lithium sulfur battery anode material, is characterized in that, the bonding agent of described step c is Kynoar or polytetrafluoroethylene.
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