CN103233246A - Method for preparing powder material with electrochemical cathode - Google Patents
Method for preparing powder material with electrochemical cathode Download PDFInfo
- Publication number
- CN103233246A CN103233246A CN2013101384019A CN201310138401A CN103233246A CN 103233246 A CN103233246 A CN 103233246A CN 2013101384019 A CN2013101384019 A CN 2013101384019A CN 201310138401 A CN201310138401 A CN 201310138401A CN 103233246 A CN103233246 A CN 103233246A
- Authority
- CN
- China
- Prior art keywords
- salt
- butyl
- negative electrode
- ammonium
- body material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of new materials, and discloses a method for preparing a powder material with an electrochemical cathode. By using an inert electrode as an anode, a massive metal, semiconductor and alloy as a cathode, and a lithium salt/sodium salt/quaternary ammonium salt organic solution, pyrrole, quaternary ammonium salt or piperidine ionic liquid or strongly alkaline water solution as an electrolyte, strong cathode polarization is carried out under constant voltage; under the action of the strong cathode voltage, the massive metal, semiconductor and alloy surface forms an unstable intermediate Mx+Ny- (M+ is an electrolyte cation, and N represents metal, semiconductor or alloy) and becomes corroded; the intermediate is very unstable in the electrolyte, and is quickly decomposed to generate an atomic cluster; the atomic cluster continues aggregate to obtain a nanoparticle sol; and finally, the sol is centrifuged/washed, and dried to obtain the powder material. The prepared powder material can be widely used in the fields of lithium ion batteries, supercapacitors, (electric) catalysis, biosensing, photovoltaic devices, micro-electronics and the like.
Description
Technical field
The present invention relates to field of new, be specifically related to the method that the electrochemistry negative electrode prepares powder body material.
Background technology
Material is the basic substance that the mankind depend on for existence and development, and the development of Materials science can promote transition of age with breakthrough, promotes human material progress and social progress, and world economy structure and social development are produced great influence.The micro/nano level powder body material can be widely used in fields such as lithium ion battery, ultracapacitor, () catalysis, bio-sensing, photovoltaic device, microelectronics.Traditional method for preparing the micro/nano level powder body material can be divided into two big classes: physical method and chemical process.Wherein physical method comprises mechanical ball milling method, mechanical crushing method, spark discharge method.These physical methods are simple to operate, cost is low, but product purity is low, and the powder body material size distribution of preparing is inhomogeneous.Chemical process comprises solution reaction method (precipitator method), hydrothermal synthesis method, gas-phase reaction method, sol-gel method, spray method and microemulsion method etc.The powder body material size distribution that these chemical processes are prepared is more even, but building-up process needs presoma salt and organic protective agent, the process relative complex, and the cost height yields poorly, and is not suitable for commercial scale production.
Compare with chemical process with these physics, electrochemical synthesis micro-/ nano powder body material has the advantage of low cost, high-level efficiency, environmental protection, is quite paid attention in scientific research and industrial application.The electrochemical method that the cathodic corrosion method is traditional relatively, more simple, quick, the synthetic materials process is presoma with the base metal, does not need presoma salt.
Summary of the invention
The objective of the invention is to: propose the method that a kind of brand-new easy cathodic corrosion block material that need not presoma salt prepares powder body material.
To achieve these goals, the technical solution adopted in the present invention is as follows:
A kind of electrochemistry negative electrode prepares the method for powder body material, may further comprise the steps:
Be anode with noble electrode (as platinum, graphite etc.), bulk metal, semi-conductor or alloy electrode are negative electrode, are electrolytic solution with in following three kinds any: the 1) organic solution of lithium salts, sodium salt, quaternary ammonium salt or pyrrolidines quaternary ammonium salt; 2) quaternary ammonium salt, pyrrolidines or piperidines ionic liquid; 3) strong alkaline aqueous solution is power supply with direct supply, under constant voltage, and reinforcing yin essence utmost point polarization, the product cleaning that negative electrode is obtained then, ultra-sonic dispersion, centrifugal, at last product is drying to obtain powder body material.
Described 1) organic solution of lithium salts, sodium salt or quaternary ammonium salt; Perhaps 2) in pyroles, quaternary ammonium salt or the piperidines ion liquid system, the metal that negative electrode adopts comprises Sn, Pb, Sb or Bi, semi-conductor comprises Te, and alloy comprises SnSb, SnPb, BiSb, SbBi, BiPb, SbTe, GeSe, SnSe, AuTe, GeTe, GaSn, AsTe, GaTe, InTe, AsTe, BiPbSn, BiSnPbCd or BiInPbSn.
Described lithium salts comprises one or more in lithium perchlorate, lithium hexafluoro phosphate, LiBF4, the lithium halide;
Described sodium salt comprises one or more in sodium perchlorate, sodium hexafluoro phosphate, sodium tetrafluoroborate, the sodium halide;
Described quaternary ammonium salt comprises: one or more in tetrabutyl ammonium halide, tetrabutyl ammonium hexafluorophosphate, tetrabutyl ammonium tetrafluoroborate, tetrabutylammonium perchlorate, tetraethyl-ammonium halide, tetraethyl-ammonium hexafluorophosphate, tetraethyl-ammonium tetrafluoroborate, tetraethyl-ammoniumper chlorate, tetramethyl-ammonium halide, tetramethyl-ammonium hexafluorophosphate, tetramethyl-ammonium tetrafluoroborate, the tetramethyl-ammoniumper chlorate;
Described pyrrolidines quaternary ammonium salt comprises: one or more in pyrrolidines halogeno salt, pyrrolidines hexafluorophosphate, pyrrolidines a tetrafluoro borate, the pyrrolidines perchlorate;
The solvent of described organic solution comprises: N, dinethylformamide, acetonitrile, propylene carbonate, dimethyl sulfoxide (DMSO), NSC 11801, diethyl carbonate, liquefied ammonia or quadrol;
Described ion liquid of quaternaries comprises: one or more in N-methoxy ethyl-diethylmethyl ammonium a tetrafluoro borate, the two trifluoromethane sulfimide salt of N-methoxy ethyl-diethylmethyl ammonium, TBuA trifluorosulfonimide salt, TBuA tosilate, TBuA hydrosulfate, TBuA dintrile amine salt, tetraethyl ammonium trifluorosulfonimide salt, tetraethyl ammonium tosilate, the tetraethyl ammonium hydrosulfate;
The pyrrolidines ionic liquid comprises: one or more in 1-butyl-1-crassitude a tetrafluoro borate, 1-butyl-1-crassitude hexafluorophosphate, 1-butyl-1-crassitude bromine salt, 1-butyl-1-crassitude villaumite, 1-butyl-1-crassitude dintrile amine salt, 1-butyl-1-crassitude nitrate, 1-normal-butyl-1-crassitude two (trifluoromethyl sulphonyl) imide, the 1-butyl-1-crassitude saccharin salt;
The piperidines ionic liquid comprises: one or more in 1-butyl-1-methyl piperidine a tetrafluoro borate, 1-butyl-1-methyl piperidine bromine salt, 1-butyl-1-methyl piperidine villaumite, 1-butyl-1-methyl piperidine dintrile amine salt, 1-butyl-1-methyl piperidine nitrate, 1-butyl-1-methyl piperidine trifluorosulfonimide salt, 1-butyl-1-methyl piperidine hexafluorophosphate, the 1-butyl-1-methyl piperidine saccharin salt.
In the strong alkaline aqueous solution system, the metal that negative electrode adopts comprises: Sn, Pb, Sb, Bi, Ni, Fe, Co, Cu, Os, Pt, Ir, Ru, Rh, Pd, Ga or In, described semi-conductor comprises Te, Ge, Si, and described alloy comprises SnSb, SnPb, BiSb, SbBi, BiPb, SbTe, GeSe, SnSe, AuTe, GeTe, GaSn, AsTe, GaTe, InTe, AsTe, PtRh, PtIr, PtRu, PtNi, AuCo, AuCu, FeCo, NiSn, BiPbSn, BiSnPbCd or BiInPbSn.
Described strong alkaline aqueous solution comprises LiOH, NaOH, KOH, NH
4OH, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or TBAH.
Electrolytical concentration is not less than 0.1mol/L in the described organic solution, and electrolytical concentration is not less than 1mol/L in the described strong alkaline aqueous solution.
The voltage Wei – 5～– 100V that adopt.
70～60 ℃ of described electrolysis temperature Wei –; Electrolysis time is 5 minutes～5 days.
The product that negative electrode obtains dehydrated alcohol, N, dinethylformamide, hydrazine hydrate or washed with de-ionized water.
In the process of preparation material, can control surface topography and the granularity of material by type, temperature of reaction, electrolysis pressurization and the interpolation tensio-active agent that changes electrolytical concentration, solvent.
In the negative electrode preparation process, bulk metal, semi-conductor and alloy surface form unsettled intermediate M in solution under the effect of reinforcing yin essence pole tension
x +N
y –(M
+Be the ionogen positively charged ion, N represents metal, semi-conductor or alloy) and corrode, this kind intermediate is very unstable in electrolytic solution, very easily decompose and produce the elementide of zero-valent state, elementide continues to reunite and just can obtain Nano sol, at last with colloidal sol centrifugal/washing, drying can obtain powder body material.Prepared powder body material can be widely used in fields such as lithium ion battery, ultracapacitor, () catalysis, bio-sensing, photovoltaic device, microelectronics.
At present, the method for electrochemical preparation powder body material mainly contains cathodic reduction and anonizing.Cathodic reduction needs presoma salt, and the powder body material of anonizing preparation is oxide compound.Electrochemistry cathodic corrosion method described herein is starting material with bulk metal, semi-conductor or alloy electrode directly, need not presoma salt, and method is more quick.
Description of drawings
Fig. 1 is the electrolytic cell device among the embodiment 1;
Fig. 2 be (a) scanning electronic microscope (SEM) of the Sn powder body material of preparation among the embodiment 1 and (b) transmission electron microscope (TEM) scheme;
Fig. 3 is the TEM figure of the Sn powder body material of preparation among the embodiment 2;
Fig. 4 is the TEM figure of the Sb powder body material of preparation among the embodiment 3;
Fig. 5 is the TEM figure of the SnSb powder body material of preparation among the embodiment 4;
Fig. 6 is selected area electron diffraction (SAED) figure of the SnSb powder body material of preparation among the embodiment 4;
Fig. 7 is the TEM figure of the SnSb powder body material of preparation among the embodiment 5;
Fig. 8 is the optical photograph of tin cathodic corrosion among the embodiment 6;
Fig. 9 is the TEM figure of the Pb powder body material of preparation among the embodiment 9;
Figure 10 is charging and discharging curve (a) and the cycle performance figure (b) of Sn powder electrode materials prepared among the embodiment 2; The button cell of illustration for being assembled into as negative material with the Sn powder body material;
Figure 11 is charging and discharging curve (a) and the cycle performance figure (b) of Sb powder electrode materials prepared among the embodiment 3.
Embodiment
Following examples are in order to explain the present invention in more detail, but these embodiment do not constitute any restriction to the present invention, and the present invention can implement by the described arbitrary mode of summary of the invention.
Embodiment 1: the cathodic corrosion metallic tin prepares the nanometer glass putty in the ionic liquid
As install shown in Figure 1, be that anode, Sn rod are negative electrode with the Pt sheet, with ionic liquid 1-normal-butyl-1-crassitude two (trifluoromethyl sulphonyl) imide as electrolytic solution, Heng Dian Ya – 20V reinforcing yin essence utmost point polarization 6h, the product that negative electrode is obtained cleans 6 times with dehydrated alcohol then, ultra-sonic dispersion (80W, 30kHz, 1min), 13300 rev/mins of high speeds are centrifugal, at last 40 ℃ of vacuum-dryings of product namely got glass putty.Fig. 2 is scanning electronic microscope (SEM) and transmission electron microscope (TEM) figure of prepared Sn powder body material.Obviously, prepared glass putty is the nanometer glass putty.
Embodiment 2: cloudy utmost point – 25V corrosion tin bar prepares the nanometer glass putty in the tetraethyl-phosphofluoric acid ammonium solution
Be that anode, Sn rod are negative electrode with the Pt sheet, in the DMF solution of 0.5mol/L tetrabutyl ammonium hexafluorophosphate, Heng Dian Ya – 25V reinforcing yin essence utmost point polarization 12h, the product that negative electrode is obtained cleans 6 times with dehydrated alcohol then, ultra-sonic dispersion (80W, 30kHz, 1min), 12000 rev/mins of high speeds are centrifugal, at last 50 ℃ of vacuum-dryings of product namely got glass putty.Show that TEM(Fig. 3) prepared glass putty is the nanometer glass putty, particle diameter is about 5nm than homogeneous.
Embodiment 3: cloudy utmost point – 25V corrosion antimony rod preparation nano stibium powder in the tetraethyl-phosphofluoric acid ammonium solution
Be that anode, Sb rod are negative electrode with the Pt sheet, in the DMF solution of 0.5mol/L tetrabutyl ammonium hexafluorophosphate, Heng Dian Ya – 25V reinforcing yin essence utmost point polarization 12h, the product that negative electrode is obtained cleans 6 times with dehydrated alcohol then, ultra-sonic dispersion (80W, 30kHz, 1min), 12000 rev/mins of high speeds are centrifugal, at last 50 ℃ of vacuum-dryings of product namely got antimony powder.Show that TEM(Fig. 4) prepared antimony powder is nano stibium powder, particle diameter is about 15nm than homogeneous.
Embodiment 4: cloudy utmost point – 25V corrosion antimony tin alloy rod preparation nanometer antimony tin alloy powder in the tetraethyl-phosphofluoric acid ammonium solution
Be that anode, SnSb rod are negative electrode with the Pt sheet, in 0.5mol/L tetrabutyl ammonium hexafluorophosphate DMF solution, Heng Dian Ya – 25V reinforcing yin essence utmost point polarization 12h, the product that negative electrode is obtained cleans 6 times with dehydrated alcohol then, ultra-sonic dispersion (80W, 30kHz, 1min), 13300 rev/mins of high speeds are centrifugal, at last 50 ℃ of vacuum-dryings of product namely got antimony tin alloy powder.Show that TEM(Fig. 5) prepared antimony tin alloy powder is nanostructure, particle diameter is about 8nm than homogeneous.Fig. 6 is corresponding selected area electron diffraction figure, by figure can, prepared SnSb powder body material is amorphous state.
Embodiment 5: cathodic corrosion antimony tin alloy rod preparation nanometer antimony tin alloy powder in the aqueous solution
Be that anode, SnSb rod are negative electrode with the Pt sheet, in the 10mol/L NaOH aqueous solution, Heng Dian Ya – 10V reinforcing yin essence utmost point polarization 0.5h, the product that negative electrode is obtained cleans 6 times ultra-sonic dispersion (95W with hydrazine hydrate washing 3 times with dehydrated alcohol then, 30kHz, 3min), 9000 rev/mins of high speeds are centrifugal, at last 50 ℃ of vacuum-dryings of product namely got antimony tin alloy powder.Show that TEM(Fig. 7) prepared antimony tin alloy powder is nanostructure, have part to reunite.
Embodiment 6: the cathodic corrosion tin bar prepares the nanometer glass putty in the piperidines ionic liquid
Be negative electrode with the Sn rod, so that piperidines ionic liquid 1-butyl-1-methyl piperidine trifluorosulfonimide salt is as electrolytic solution, other condition is with embodiment one.Fig. 8 is cathodic corrosion process photo, divides a large amount of black precipitates that shed as can be seen, and black precipitate can be obtained glass putty by embodiment 1 washing, drying.Compare with embodiment 1, the speed for preparing in this kind electrolytic solution is slower.
Embodiment 7: the cathodic corrosion tin bar prepares the nanometer glass putty in the ion liquid of quaternaries
Be negative electrode with the Sn rod, as electrolytic solution, other condition is with embodiment 1 and embodiment 6 with ion liquid of quaternaries N-methoxy ethyl-diethylmethyl ammonium a tetrafluoro borate.Similar among the product for preparing in this system and the embodiment 6, but preparation process is slower.
Embodiment 8: the cathodic corrosion lead rod prepares the nanometer lead powder in the pyrrolidines quaternary ammonium salt
Be negative electrode with the Pb rod, as electrolytic solution, other condition is with embodiment 4 with the DMF solution of pyrrolidines quaternary ammonium salt 1-butyl-1-crassitude bromide.By TEM(Fig. 9) prepared as can be known Pb powder is the nanometer lead powder.
Embodiment 9: cathodic corrosion antimony rod preparation nano stibium powder in the lithium salts
Be that anode, Sb rod are negative electrode with the Pt sheet, with 1mol/L LiPF
6Propylene carbonate (PC) solution as electrolytic solution, permanent electricity is pressed – 10V reinforcing yin essence utmost point polarization 24h, a small amount of antimony comes off from the antimony rod, the antimony rod behind the cathodic polarization 24h is transferred in the 4mol/L NaOH aqueous solution can divides the antimony that sheds a large amount of colloidal sol.Antimony colloidal sol is pressed method washing, the drying described in the embodiment 5, can obtain antimony powder.
Embodiment 10: cathodic corrosion antimony rod preparation nano stibium powder in the sodium salt
With 1mol/L NaClO
4Propylene carbonate (PC) solution as electrolytic solution, other condition is with embodiment 9, reinforcing yin essence utmost point polarization 5h, a small amount of antimony comes off from the antimony rod, the antimony rod behind the cathodic polarization 5h is transferred in the 4mol/L NaOH aqueous solution can divides the antimony that sheds a large amount of colloidal sol.Antimony colloidal sol is pressed method washing, the drying described in embodiment 5 or the embodiment 9, can obtain antimony powder.The speed of preparation antimony powder is than fast in the embodiment 9 described lithium salts in this sodium salt.
Embodiment 11: the application of nanometer glass putty in lithium ion battery negative material
The nanometer tin powder that obtains with embodiment 2, conductive agent acetylene black is dissolved in N-Methyl pyrrolidone with binding agent PVDF() become uniform sizing material by mass ratio 80:10:10 mixed grinding, be applied on the clean Copper Foil and make electrode film, predrying under 75 ℃ then, obtain negative plate 120 ℃ of following vacuum-dryings again.Do anodal with the lithium sheet.Adopt 1mol/L LiPF
6/ NSC 11801 (EC)+dimethyl carbonate (DMC) (volume ratio=1:1) as electrolytic solution.In the argon gas glove box, be assembled into CR2016 button cell (illustration 10a).Adopt CT2001A type constant current charge-discharge instrument (Wuhan is blue) to carry out the test of constant current cycle performance, charging and discharging currents density is 100mA/g, and the charging/discharging voltage scope is controlled between 0.01～2V.Figure 10 a is the preceding voltage-capacity curve that charges and discharge circulation for twice, lithiumation and the peak that goes lithiumation be complicated (and not obvious) comparatively, peak 1.35V, the 1.2V that occurs more than 0.8V and 0.95V can ascribe the formation of SEI film to, and peak 0.6V, the 0.3V that occurs below 0.8V and 0.15V can sum up lithium and tin alloying reaction in various degree.By capacity cyclic curve (Figure 10 b) as can be known, the synthetic glass putty of this method has bigger discharge first and charging capacity, is respectively 1213.6 and 883.6mAh/g.Circulate after ten times, loading capacity also has 643.9mAh/g.
Embodiment 12: the application of nano stibium powder in lithium ion battery negative material
The nano stibium powder end that obtains with embodiment 3, conductive agent acetylene black is dissolved in N-Methyl pyrrolidone with binding agent PVDF() become uniform sizing material by mass ratio 80:10:10 mixed grinding, be applied on the clean Copper Foil and make electrode film, predrying under 75 ℃ then, obtain negative plate 120 ℃ of following vacuum-dryings again.Do anodal with the lithium sheet.Adopt 1mol/L LiPF
6/ fluorinated ethylene carbonate (FEC)+NSC 11801 (EC)+dimethyl carbonate (DMC) (volume ratio=10:45:45) as electrolytic solution.In the argon gas glove box, be assembled into the CR2016 button cell.Adopt CT2001A type constant current charge-discharge instrument (Wuhan is blue) to carry out the test of constant current cycle performance, charging and discharging currents density is 0.1C(1C=660mA/g), the charging/discharging voltage scope is controlled between 0.01～2V.(Figure 11 two discharge platforms occur at 1.35V and 0.75V a) as can be known, corresponds respectively to the lithiumation of the weisspiessglanz that the antimony powder surface forms and the lithiumation of metallic state antimony powder by the voltage-capacity curve that charges and discharge circulation for preceding twice.By capacity cyclic curve (Figure 11 b) as can be known, the synthetic glass putty of this method has higher discharge first and charging capacity, is respectively 797.0 and 411.1mAh/g.Circulate after 34 times, capacity also has 399.9mAh/g, and the synthetic antimony powder of this explanation has better cycle performance.
Claims (9)
1. an electrochemistry negative electrode prepares the method for powder body material, it is characterized in that, may further comprise the steps:
Be anode with the noble electrode, bulk metal, semi-conductor or alloy electrode are negative electrode, are electrolytic solution with in following three kinds any: the 1) organic solution of lithium salts, sodium salt, quaternary ammonium salt or pyrrolidines quaternary ammonium salt; 2) quaternary ammonium salt, pyrrolidines or piperidines ionic liquid; 3) strong alkaline aqueous solution is power supply with direct supply, under constant voltage, and reinforcing yin essence utmost point polarization, the product cleaning that negative electrode is obtained then, ultra-sonic dispersion, centrifugal, at last product is drying to obtain powder body material.
2. electrochemistry negative electrode according to claim 1 prepares the method for powder body material, it is characterized in that, described 1) organic solution of lithium salts, sodium salt or quaternary ammonium salt; Perhaps 2) in pyroles, quaternary ammonium salt or the piperidines ion liquid system, the metal that negative electrode adopts comprises Sn, Pb, Sb or Bi, semi-conductor comprises Te, and alloy comprises SnSb, SnPb, BiSb, SbBi, BiPb, SbTe, GeSe, SnSe, AuTe, GeTe, GaSn, AsTe, GaTe, InTe, AsTe, BiPbSn, BiSnPbCd or BiInPbSn.
3. electrochemistry negative electrode according to claim 1 and 2 prepares the method for powder body material, it is characterized in that, described lithium salts comprises one or more in lithium perchlorate, lithium hexafluoro phosphate, LiBF4, the lithium halide;
Described sodium salt comprises one or more in sodium perchlorate, sodium hexafluoro phosphate, sodium tetrafluoroborate, the sodium halide;
Described quaternary ammonium salt comprises: one or more in tetrabutyl ammonium halide, tetrabutyl ammonium hexafluorophosphate, tetrabutyl ammonium tetrafluoroborate, tetrabutylammonium perchlorate, tetraethyl-ammonium halide, tetraethyl-ammonium hexafluorophosphate, tetraethyl-ammonium tetrafluoroborate, tetraethyl-ammoniumper chlorate, tetramethyl-ammonium halide, tetramethyl-ammonium hexafluorophosphate, tetramethyl-ammonium tetrafluoroborate, the tetramethyl-ammoniumper chlorate;
Described pyrrolidines quaternary ammonium salt comprises: one or more in pyrrolidines halogeno salt, pyrrolidines hexafluorophosphate, pyrrolidines a tetrafluoro borate, the pyrrolidines perchlorate;
The solvent of described organic solution comprises: N, dinethylformamide, acetonitrile, propylene carbonate, dimethyl sulfoxide (DMSO), NSC 11801, diethyl carbonate, liquefied ammonia or quadrol;
Described ion liquid of quaternaries comprises: one or more in N-methoxy ethyl-diethylmethyl ammonium a tetrafluoro borate, the two trifluoromethane sulfimide salt of N-methoxy ethyl-diethylmethyl ammonium, TBuA trifluorosulfonimide salt, TBuA tosilate, TBuA hydrosulfate, TBuA dintrile amine salt, tetraethyl ammonium trifluorosulfonimide salt, tetraethyl ammonium tosilate, the tetraethyl ammonium hydrosulfate;
The pyrrolidines ionic liquid comprises: one or more in 1-butyl-1-crassitude a tetrafluoro borate, 1-butyl-1-crassitude hexafluorophosphate, 1-butyl-1-crassitude bromine salt, 1-butyl-1-crassitude villaumite, 1-butyl-1-crassitude dintrile amine salt, 1-butyl-1-crassitude nitrate, 1-normal-butyl-1-crassitude two (trifluoromethyl sulphonyl) imide, the 1-butyl-1-crassitude saccharin salt;
The piperidines ionic liquid comprises: one or more in 1-butyl-1-methyl piperidine a tetrafluoro borate, 1-butyl-1-methyl piperidine bromine salt, 1-butyl-1-methyl piperidine villaumite, 1-butyl-1-methyl piperidine dintrile amine salt, 1-butyl-1-methyl piperidine nitrate, 1-butyl-1-methyl piperidine trifluorosulfonimide salt, 1-butyl-1-methyl piperidine hexafluorophosphate, the 1-butyl-1-methyl piperidine saccharin salt.
4. electrochemistry negative electrode according to claim 1 prepares the method for powder body material, it is characterized in that, in the strong alkaline aqueous solution system, the metal that negative electrode adopts comprises: Sn, Pb, Sb, Bi, Ni, Fe, Co, Cu, Os, Pt, Ir, Ru, Rh, Pd, Ga or In, described semi-conductor comprises Te, Ge, Si, described alloy comprises SnSb, SnPb, BiSb, SbBi, BiPb, SbTe, GeSe, SnSe, AuTe, GeTe, GaSn, AsTe, GaTe, InTe, AsTe, PtRh, PtIr, PtRu, PtNi, AuCo, AuCu, FeCo, NiSn, BiPbSn, BiSnPbCd or BiInPbSn.
5. prepare the method for powder body material according to claim 1 or 4 described electrochemistry negative electrodes, it is characterized in that described strong alkaline aqueous solution comprises LiOH, NaOH, KOH, NH
4OH, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or TBAH.
6. electrochemistry negative electrode according to claim 1 prepares the method for powder body material, it is characterized in that, electrolytical concentration is not less than 0.1mol/L in the described organic solution, and electrolytical concentration is not less than 1mol/L in the described strong alkaline aqueous solution.
7. electrochemistry negative electrode according to claim 1 prepares the method for powder body material, it is characterized in that, the voltage Wei – 5～– 100V that adopt.
8. electrochemistry negative electrode according to claim 1 prepares the method for powder body material, it is characterized in that, 70～60 ℃ of described electrolysis temperature Wei –; Electrolysis time is 5 minutes～5 days.
9. electrochemistry negative electrode according to claim 1 prepares the method for powder body material, it is characterized in that, the product that negative electrode obtains dehydrated alcohol, N, dinethylformamide, hydrazine hydrate or washed with de-ionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310138401.9A CN103233246B (en) | 2013-04-19 | 2013-04-19 | A kind of electrochemical cathode prepares the method for powder body material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310138401.9A CN103233246B (en) | 2013-04-19 | 2013-04-19 | A kind of electrochemical cathode prepares the method for powder body material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103233246A true CN103233246A (en) | 2013-08-07 |
| CN103233246B CN103233246B (en) | 2016-02-24 |
Family
ID=48881310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310138401.9A Active CN103233246B (en) | 2013-04-19 | 2013-04-19 | A kind of electrochemical cathode prepares the method for powder body material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103233246B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368357A (en) * | 2014-09-24 | 2015-02-25 | 中国科学技术大学 | Pd@PtNi/C metal nano-catalyst, and preparation method and use thereof |
| CN106544699A (en) * | 2017-01-03 | 2017-03-29 | 昆明理工大学 | A kind of method that ionic liquid electrolytic recovery waste lead accumulator lead plaster carries lead |
| CN107820521A (en) * | 2015-06-12 | 2018-03-20 | 帝国革新有限公司 | The electrochemistry recycling of plumbum-based material |
| CN109321940A (en) * | 2018-11-30 | 2019-02-12 | 西南大学 | A kind of the electrochemical oxidation synthetic method and its application of amide |
| CN110240906A (en) * | 2018-03-07 | 2019-09-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Group III-V semiconductor etching liquid and its preparation method and application |
| US10424775B2 (en) | 2016-06-28 | 2019-09-24 | Samsung Electronics Co., Ltd. | Lithium battery and method of manufacturing the same |
| CN110407183A (en) * | 2019-07-31 | 2019-11-05 | 兰州大学 | A kind of tellurium nanometer rods, energy storage device and preparation method thereof, the method for preparing tellurium nano material |
| CN112811401A (en) * | 2021-01-11 | 2021-05-18 | 厦门大学 | Preparation method for obtaining few-layer two-dimensional tellurine in large quantity |
| CN112829151A (en) * | 2020-12-16 | 2021-05-25 | 东北林业大学 | Method for preparing InSe thin film through electrochemical intercalation |
| CN113564382A (en) * | 2021-07-09 | 2021-10-29 | 中南大学 | Method for preparing metal aluminum by reduction at room temperature |
| EP4081668A4 (en) * | 2020-03-06 | 2023-10-11 | The Board of Regents of The Nevada System of Higher Education on behalf of the University of Nevada, Las Vegas | Lithium recovery from lithium salts dissolved in ionic liquids |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106788A (en) * | 1984-10-29 | 1986-05-24 | Toppan Printing Co Ltd | Metal collecting method and its device |
| CN1676670A (en) * | 2005-01-04 | 2005-10-05 | 华南理工大学 | Method for continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave |
| CN102732915A (en) * | 2011-04-13 | 2012-10-17 | 中国科学院过程工程研究所 | Ionic liquid electrolysis method for preparing micro-nano aluminum powder |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
-
2013
- 2013-04-19 CN CN201310138401.9A patent/CN103233246B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106788A (en) * | 1984-10-29 | 1986-05-24 | Toppan Printing Co Ltd | Metal collecting method and its device |
| CN1676670A (en) * | 2005-01-04 | 2005-10-05 | 华南理工大学 | Method for continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave |
| CN102732915A (en) * | 2011-04-13 | 2012-10-17 | 中国科学院过程工程研究所 | Ionic liquid electrolysis method for preparing micro-nano aluminum powder |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
Non-Patent Citations (1)
| Title |
|---|
| 杨应昌: ""几种微/纳米金属及金属氧化物功能材料的电化学制备、表征及应用"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368357A (en) * | 2014-09-24 | 2015-02-25 | 中国科学技术大学 | Pd@PtNi/C metal nano-catalyst, and preparation method and use thereof |
| CN104368357B (en) * | 2014-09-24 | 2016-04-20 | 中国科学技术大学 | A kind of PdPtNi/C metal nano Catalysts and its preparation method and purposes |
| CN107820521B (en) * | 2015-06-12 | 2021-03-30 | 帝国大学创新有限公司 | Electrochemical recycling of lead-based materials |
| CN107820521A (en) * | 2015-06-12 | 2018-03-20 | 帝国革新有限公司 | The electrochemistry recycling of plumbum-based material |
| US10424775B2 (en) | 2016-06-28 | 2019-09-24 | Samsung Electronics Co., Ltd. | Lithium battery and method of manufacturing the same |
| CN106544699A (en) * | 2017-01-03 | 2017-03-29 | 昆明理工大学 | A kind of method that ionic liquid electrolytic recovery waste lead accumulator lead plaster carries lead |
| CN110240906A (en) * | 2018-03-07 | 2019-09-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Group III-V semiconductor etching liquid and its preparation method and application |
| CN109321940A (en) * | 2018-11-30 | 2019-02-12 | 西南大学 | A kind of the electrochemical oxidation synthetic method and its application of amide |
| CN110407183A (en) * | 2019-07-31 | 2019-11-05 | 兰州大学 | A kind of tellurium nanometer rods, energy storage device and preparation method thereof, the method for preparing tellurium nano material |
| EP4081668A4 (en) * | 2020-03-06 | 2023-10-11 | The Board of Regents of The Nevada System of Higher Education on behalf of the University of Nevada, Las Vegas | Lithium recovery from lithium salts dissolved in ionic liquids |
| CN112829151A (en) * | 2020-12-16 | 2021-05-25 | 东北林业大学 | Method for preparing InSe thin film through electrochemical intercalation |
| CN112811401A (en) * | 2021-01-11 | 2021-05-18 | 厦门大学 | Preparation method for obtaining few-layer two-dimensional tellurine in large quantity |
| CN113564382A (en) * | 2021-07-09 | 2021-10-29 | 中南大学 | Method for preparing metal aluminum by reduction at room temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103233246B (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103233246B (en) | A kind of electrochemical cathode prepares the method for powder body material | |
| Song et al. | Crossroads in the renaissance of rechargeable aqueous zinc batteries | |
| Blanc et al. | Scientific challenges for the implementation of Zn-ion batteries | |
| Jia et al. | Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries | |
| Wan et al. | Energy storage chemistry in aqueous zinc metal batteries | |
| Li et al. | Developing cathode materials for aqueous zinc ion batteries: challenges and practical prospects | |
| Chen et al. | Ultrastable and high-performance Zn/VO2 battery based on a reversible single-phase reaction | |
| CN103441260B (en) | A kind of aqueous alkaline electrochemical energy storing device | |
| CN102024996A (en) | High-performance rechargeable magnesium battery and manufacturing method thereof | |
| Yu et al. | The applications of semiconductor materials in air batteries | |
| Lu et al. | Engineering metal selenides for sodium-and potassium-ion batteries | |
| CN105514421B (en) | A kind of modified oxidized nickel negative electrode material and preparation method thereof | |
| Yang et al. | Anode-free sodium metal batteries as rising stars for lithium-ion alternatives | |
| CN106058213B (en) | A kind of two stannic selenides/polyethyleneimine composite material and its preparation method and application | |
| Karuppasamy et al. | Nanostructured transition metal sulfide/selenide anodes for high-performance sodium-ion batteries | |
| Xie et al. | Advancements in achieving high reversibility of zinc anode for alkaline zinc‐based batteries | |
| Chen et al. | The critical role of aluminum sulfate as electrolyte additive on the electrochemical performance of lead-acid battery | |
| Song et al. | Steric-hindrance effect and self-sacrificing template behavior induced PDA@ SnO2-QDs/N-doped carbon hollow nanospheres: enhanced structural stability and reaction kinetics for long-cyclic Li-ion half/full batteries | |
| Meng et al. | The investigation on the electrochemical performance of CuI as cathode material for zinc storage | |
| Mao et al. | 2D V10O24· nH2O sheets as a high-performance cathode material for aqueous zinc-ion batteries | |
| CN112234195A (en) | Chargeable and dischargeable water system zinc ion full cell | |
| CN106449153B (en) | A kind of Ni nanoparticle (OH)2@C composites and preparation method | |
| KR20070069306A (en) | Fabrication method of nano-sized active materials containing copper phase with improved cycle-ability for anode of lithium secondary battery | |
| CN103647068B (en) | A kind of preparation method of anode material of lithium-ion battery | |
| CN103198935A (en) | Preparation method of graphene sheet modified spinel type lithium manganate or alpha type manganese dioxide electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |