CN101831677A - Method for electrodepositing lithium-copper alloy in ionic liquid system - Google Patents
Method for electrodepositing lithium-copper alloy in ionic liquid system Download PDFInfo
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- CN101831677A CN101831677A CN201010301352A CN201010301352A CN101831677A CN 101831677 A CN101831677 A CN 101831677A CN 201010301352 A CN201010301352 A CN 201010301352A CN 201010301352 A CN201010301352 A CN 201010301352A CN 101831677 A CN101831677 A CN 101831677A
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Abstract
The invention discloses a method for electrodepositing a lithium-copper alloy in an ionic liquid system, which relates to a method for electrodepositing the lithium-copper alloy. The method solves the problems that the conventional smelting method for preparing the lithium-copper alloy cannot control the lithium element content easily and has high energy consumption. The method comprises the following: step one, adding LiBF4, Cu(BF4)2 and an additive into BMIMBF4 in turn to prepare an electrolyte; and step two, immerging an anode material and a cathode material into the electrolyte, and adopting a constant current mode and controlling the current density and the electrodepositing time to realize the preparation of the lithium-copper alloy, wherein the two steps are performed in a glove box. The method has the advantages of concise process, simple equipment and low energy consumption; the metal lithium content in the lithium-copper alloy is adjusted and controlled by adjusting components and electrodepositing technological parameters of the electrolyte; the metal lithium content is controllable; and the atomic mass percent content is 7 to 40 percent. Simultaneously, the method realizes co-deposition of lithium and copper which have large electrode potential differences; and the obtained lithium-copper alloy can be used as a cathode material for a lithium ion battery.
Description
Technical field
The present invention relates to a kind of method of galvanic deposit lithium-copper alloy.
Background technology
At present, the research of lithium-copper alloy is mainly used in two big fields, and a class is to add the lithium-copper alloy of high-content lithium, mainly utilize the shielding effect of lithium to neutron, as the shielding material of nuclear reactor, another kind of then is the lithium-copper alloy that adds micro-lithium, mainly as height lead, high-strength, high-wear-resistant alloy.Japan and the United States, Su Sanguo be at the research lithium-copper alloy, wherein the massfraction of lithium between 0.01%～1.3%, the welding wire, electric welding that this alloy is mainly used in copper conductor, bit copper with electrode, the aspects such as contact material of arc extinguishing effect are arranged.There is report to show that lithium-copper alloy can well be used in fusion reactor; After adding lithium in small amounts and other element in the copper base superconducting alloy, it is better to obtain superconductivity, the material that processing characteristics is superior.This shows that lithium-copper alloy has very wide application prospect.
At present, the preparation of lithium-copper alloy obtains by the melting mode mostly.But (the former is 8.9g/cm owing to copper, lithium density differ greatly
3, the latter only is 0.534g/cm
3), in melting, casting cycle, be difficult to density great disparity two kinds of big Metal Melting like this are smelt macroscopic view distribution alloy comparatively uniformly, thereby smelting process is difficult to obtain the cupralith of chemical ingredients uniformity.Because the chemically reactive of lithium is bigger, at high temperature can with many substance reactions, lithium joined will to avoid oxidation, nitrogenize in the copper liquid be a difficult point of smelting process, and lithium can react also with materials such as watering injection molding and crucible, thereby smelting process is introduced impurity easily when the preparation lithium-copper alloy.In addition, the loss of lithium is difficult to determine in fusion process, thereby adopts smelting process to be difficult to obtain the more stable cupralith of lithium content.And adopt the method for galvanic deposit to prepare the above-mentioned shortcoming that lithium-copper alloy can overcome smelting process just.
As everyone knows, metallic lithium is very active, can violent reaction take place with water, therefore, can't carry out the galvanic deposit of lithium in the aqueous solution.Adopt organic electrolyte and il electrolyte electrodeposit metals lithium, currently reported.But with the ionic liquid is that electrolytic solution electrodeposited electrode electromotive force differs the bigger lithium and the alloy of copper, yet there are no report.
Summary of the invention
The objective of the invention is in order to solve in the existing smelting method for preparing lithium-copper alloy elemental lithium content waywardly, the problem that energy consumption is big the invention provides the method for galvanic deposit lithium-copper alloy in a kind of ion liquid system.
The method of galvanic deposit lithium-copper alloy realizes by following steps in a kind of ion liquid system of the present invention: one, with LiBF
4, Cu (BF
4)
2Add ionic liquid 1-butyl 3-methyl imidazolium tetrafluoroborate (BMIMBF successively with additive
4) in, stirring and dissolving gets electrolytic solution, wherein LiBF
4Concentration be 40～160g/L, Cu (BF
4)
2Concentration be that 100～200g/L, additive account for 0.5%～2% of electrolytic solution total mass, described additive is a butynediol; Two, after the anticathode material carries out the galvanic deposit pre-treatment, cathode material and anode material are immersed in the electrolytic solution simultaneously, adopt the continuous current mode to carry out galvanic deposit 10～120min, promptly obtain lithium-copper alloy on the cathode material surface; Wherein, control current density is 5～10A/m in the step 2
2, cathode material is copper, nickel, titanium or stainless steel etc., anode material is copper, platinum or graphite etc., keeps electrolyte temperature at 20～50 ℃; Step 1 and step 2 are all carried out in being full of the glove box of rare gas element.
Cathode material and anode material are not limited to the above material of enumerating among the present invention, and the material that every existing electro-deposition techniques field can be used as cathode material all can be used for the present invention, and this area inert anode material commonly used also can be used for the present invention.
Method of the present invention is simple, and technology is terse, and equipment is simple, and the envrionment conditions of preparation requires low, and energy consumption is low.Realized having the lithium of big electrode potential difference and the codeposition of copper simultaneously, and the lithium-copper alloy coating that obtains of galvanic deposit evenly, have metalluster, thickness is 1～10 μ m; The present invention can adjust the content of metallic lithium in the lithium-copper alloy by adjusting electrolytic solution composition concentration and every electro-deposition process parameter, and metallic lithium content is controlled, and the atomic mass percentage composition of lithium is 7%～40% in the lithium-copper alloy.
The present invention adopts ionic liquid as solvent, obtains the nonaqueous electrolyte liquid system, has avoided can't realizing in the aqueous solution because of metallic lithium and water generation vigorous reaction the drawback of metallic lithium galvanic deposit.
Under 298.15K, aqueous conditions, the Standard Electrode Potentials of copper is 0.337V, and the Standard Electrode Potentials of lithium is-3.045V.Both potential differences are 3.382V, under existing those skilled in the art's common practise " one of condition of electroplating two kinds of metals of codeposition is that the electrode potential of two kinds of metals of codeposition is close or equal ", the deposition of lithium and copper can't realize, and the present invention jumps out the consistent research means of existing this area, in ion liquid system, realize the codeposition of lithium and copper, obtained lithium-copper alloy coating.
The ionic liquid at room temperature that the present invention adopts has good solubility to most of inorganicss and organism, and it also has very wide electrochemical window, good electroconductibility, does not almost have vapour pressure, higher advantages such as thermostability simultaneously.Therefore, ionic liquid is subjected to people's extensive attention just day by day as the green solvent of a new generation.
For electrodeposit metals, because ionic liquid has very wide electrochemical window, the metal codeposition in ionic liquid that so just makes two kinds of electrode potentials differ bigger becomes possibility, therefore, has realized the galvanic deposit of lithium-copper alloy in il electrolyte.
The present invention obtains lithium-copper alloy and can be applicable to lithium ion battery negative material.
Description of drawings
Fig. 1 is the SEM microscopic appearance figure of lithium-copper alloy in the embodiment 18; Fig. 2 is the SEM microscopic appearance figure of the lithium-copper alloy that the contrast experiment obtains in the embodiment 18.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for galvanic deposit lithium-copper alloy realizes by following steps in the present embodiment ion liquid system: one, with LiBF
4, Cu (BF
4)
2Add ionic liquid 1-butyl 3-methyl imidazolium tetrafluoroborate (BMIMBF successively with additive
4) in, stirring and dissolving gets electrolytic solution, wherein LiBF
4Concentration be 40～160g/L, Cu (BF
4)
2Concentration be that 100～200g/L, additive account for 0.5%～2% of electrolytic solution total mass, described additive is a butynediol; Two, after the anticathode material carries out the galvanic deposit pre-treatment, cathode material and anode material are immersed in the electrolytic solution simultaneously, adopt the continuous current mode to carry out galvanic deposit 10～120min, promptly obtain lithium-copper alloy on the cathode material surface; Wherein, control current density is 5～10A/m in the step 2
2, cathode material is copper, nickel, titanium or stainless steel, anode material is copper, platinum or graphite, keeps electrolyte temperature at 20～50 ℃; Step 1 and step 2 are all carried out in being full of the glove box of rare gas element.
Present embodiment step 1 and step 2 be full of argon gas or helium glove box in carry out.
After the present embodiment step 2 is finished, cathode material is taken out, use ethanol, washed with de-ionized water, seasoning more then successively.
The present embodiment method is simple, and technology is terse, and equipment is simple, and the envrionment conditions of preparation requires low, and energy consumption is low.The present invention can adjust the content of metallic lithium in the lithium-copper alloy, wherein LiBF in the electrolyte component by adjusting electrolytic solution composition concentration and every electro-deposition process parameter
4Concentration bigger to the metallic lithium content influence, metallic lithium content is controlled, the atomic mass percentage composition of lithium is 7%～40% in the lithium-copper alloy.
Realized having the lithium of big electrode potential difference and the codeposition of copper simultaneously, and the lithium-copper alloy coating that obtains of galvanic deposit evenly, have metalluster.
Present embodiment intermediate ion liquid (Ionic liquid) is meant the organic liquid material of being made up of ion fully under room temperature and close temperature, be also referred to as room temperature melting salt (Room temperature molten salts).It and traditional " melting salt " are essentially different, because ionic liquid is not to form by high temperature melt.Form ion liquid positively charged ion and be generally organic alkyl imidazole, alkyl pyridine, quaternary amine etc., negatively charged ion is generally Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, N (CN)
2-Deng.Huge positively charged ion in the ionic liquid and negatively charged ion have the height asymmetry, because steric restriction makes the yin, yang ion be difficult to close-packed on microcosmic, thereby hinders its crystallization, make the fusing point of this ionic compound descend, can exist with the form of liquid at a lower temperature.At present, ionic liquid is applied in every field such as extracting and separating, organic reaction, electrochemistry, catalyzer widely.
Embodiment two: that present embodiment and embodiment one are different is LiBF in the step 1
4Concentration be 80～120g/L.Other step and parameter are identical with embodiment one.
Embodiment three: that present embodiment and embodiment one are different is LiBF in the step 1
4Concentration be 100g/L.Other step and parameter are identical with embodiment one.
Embodiment four: Cu (BF in present embodiment and embodiment one, two or three different steps one
4)
2Concentration be 120～180g/L.Other step and parameter are identical with embodiment one, two or three.
Embodiment five: that present embodiment and embodiment one, two or three are different is Cu (BF in the step 1
4)
2Concentration be 150g/L.Other step and parameter are identical with embodiment one, two or three.
Embodiment six: present embodiment and embodiment one to five are different be that additive accounts for the electrolytic solution total mass in the step 1 0.8%～1.5%.Other step and parameter are identical with embodiment one to five.
Embodiment seven: present embodiment and embodiment one to five are different be that additive accounts for the electrolytic solution total mass in the step 1 1%.Other step and parameter are identical with embodiment one to five.
Embodiment eight: present embodiment and embodiment one to seven are different is that galvanic deposit pre-treatment in the step 2 is followed successively by conventional alkaline degreasing, the 20%HCl solution acid pickling, and washing then, dry again.Other step and parameter are identical with embodiment one to seven.
Conventional alkaline degreasing is operating as in the present embodiment: (1) is containing yellow soda ash 20gL
-1, sodium phosphate 20gL
-1With water glass 20gL
-1Degreasing fluid in oil removing 10min, the degreasing fluid temperature is 80 ℃; Perhaps (2) are containing sodium hydroxide 80gL
-1, yellow soda ash 30gL
-1, sodium phosphate 60gL
-1, water glass 10/gL
-1Degreasing fluid in oil removing 10min, the degreasing fluid temperature is 90 ℃.Conventional oil removing is not limited to above-mentioned two kinds, and every this area oil removing mode commonly used all can be used for present embodiment.
Embodiment nine: what present embodiment and embodiment one to eight were different is to adopt the continuous current mode to carry out galvanic deposit 30～80min in the step 2.Other step and parameter are identical with embodiment one to eight.
Embodiment ten: what present embodiment and embodiment one to eight were different is to adopt the continuous current mode to carry out galvanic deposit 40min in the step 2.Other step and parameter are identical with embodiment one to eight.
Embodiment 11: what present embodiment and embodiment one to ten were different is that control current density is 6～9A/m in the step 2
2Other step and parameter are identical with embodiment one to ten.
Embodiment 12: what present embodiment and embodiment one to ten were different is that control current density is 8A/m in the step 2
2Other step and parameter are identical with embodiment one to ten.
Embodiment 13: what present embodiment and embodiment one to 12 were different is to keep electrolyte temperature at 25～40 ℃ in the step 2.Other step and parameter are identical with embodiment one to 12.
Embodiment 14: what present embodiment and embodiment one to 12 were different is to keep electrolyte temperature at 30 ℃ in the step 2.Other step and parameter are identical with embodiment one to 12.
Embodiment 15: the method for galvanic deposit lithium-copper alloy realizes by following steps in the present embodiment ion liquid system: one, with LiBF
4, Cu (BF
4)
2, the additive butynediol adds ionic liquid 1-butyl 3-methyl imidazolium tetrafluoroborate (BMIMBF successively
4) in, stirring and dissolving gets electrolytic solution, wherein LiBF
4Concentration be 40g/L, Cu (BF
4)
2Concentration be that 150g/L, additive account for 0.5% of electrolytic solution total mass; Two, electrolytic copper foil is carried out the galvanic deposit pre-treatment after, electrolytic copper foil is immersed in the electrolytic solution as negative electrode, and then copper sheet immersed in the electrolytic solution as anode, adopt the continuous current mode to carry out galvanic deposit 40min, use ethanol, washed with de-ionized water successively after then electrolytic copper foil being taken out, promptly get lithium-copper alloy; Wherein, control current density is 5A/m in the step 1
2, cathode and anode spacing is 1cm, keeps electrolyte temperature at 30 ℃; Step 1 and step 2 are carried out in being full of the glove box of argon gas.
The galvanic deposit pre-treatment is followed successively by conventional alkaline degreasing (at yellow soda ash 20gL in the present embodiment step 2
-1, sodium phosphate 20gL
-1, water glass 20/gL
-1Degreasing fluid in oil removing 10min, the degreasing fluid temperature is 80 ℃), the 20%HCl solution acid pickling, washing then, dry again.
The thickness that present embodiment obtains lithium-copper alloy coating is about 2 μ m, coating evenly, have metalluster, the atomic percentage conc of Li is 7% (quality) in plasma emission spectrometer (ICP) the test result coating.
The ICP means of testing is in the present embodiment: coating is dissolved in rare nitric acid is mixed with solution, adopt German PerkinElmer5300DV plasma emission spectrometer (ICP) to measure the content of elemental lithium and copper in the solution.
Embodiment 16: what present embodiment and embodiment 15 were different is that additive is a butynediol in the step 1, LiBF
4Concentration be 100g/L, Cu (BF
4)
2Concentration be that 200g/L, additive account for 1% of electrolytic solution total mass; Cathode material adopts nickel foil in the step 2, galvanic deposit 20min, and control current density is 8A/m
2, cathode and anode spacing is 3cm, keeps electrolyte temperature at 20 ℃.
The thickness that present embodiment obtains lithium-copper alloy coating is about 1.4 μ m, coating evenly, have metalluster, the atomic percentage conc of Li is 23.8% (quality) in the ICP test result coating.The ICP means of testing is identical with embodiment 15.
Embodiment 17: what present embodiment and embodiment 15 were different is that additive is a butynediol in the step 1, LiBF
4Concentration be 160g/L, Cu (BF
4)
2Concentration be that 150g/L, additive account for 2% of electrolytic solution total mass; Cathode material adopts stainless steel in the step 2, galvanic deposit 20min, and control current density is 10A/m
2, cathode and anode spacing is 5cm, keeps electrolyte temperature at 40 ℃.
The thickness that present embodiment obtains lithium-copper alloy coating is about 2 μ m, coating evenly, have metalluster, the atomic percentage conc of Li is 39.8% (quality) in the ICP test result coating.The ICP means of testing is identical with embodiment 15.
Embodiment 18: what present embodiment and embodiment 15 were different is that additive is a butynediol in the step 1, LiBF
4Concentration be 160g/L, Cu (BF
4)
2Concentration be that 200g/L, butynediol account for 0.5% of electrolytic solution total mass; Cathode material adopts Copper Foil in the step 2, galvanic deposit 30min, and control current density is 8A/m
2, cathode and anode spacing is 2cm, keeps electrolyte temperature at 40 ℃.
The thickness that present embodiment obtains lithium-copper alloy coating is about 1.7 μ m, coating evenly, have metalluster, the atomic percentage conc of Li is 37.2% (quality) in the ICP test result coating.The ICP means of testing is identical with embodiment 15.
The scanning electronic microscope of the lithium-copper alloy that present embodiment obtains (SEM) shape appearance figure, as shown in Figure 1.As seen from Figure 1, the crystallization of the lithium-copper alloy that obtains is tiny, and densification is evenly distributed.
As a comparison, carry out following contrast experiment, the additive butynediol in the electrolytic solution composition of present embodiment is removed, all the other electrolytic solution compositions and concentration are constant, and the anode and cathode material is constant, galvanic deposit parameter (depositing time, current density, cathode and anode spacing) constant, carry out the continuous current galvanic deposit.The scanning electronic microscope of the lithium-copper alloy that obtains (SEM) shape appearance figure, as shown in Figure 2.As seen from Figure 2, the crystallization of the lithium-copper alloy for preparing in not having the electrolytic solution of additive is thick, and is loose, and skewness.
As seen, additive has very big influence to the microstructure of the lithium-copper alloy of present embodiment, and when adopting butynediol as additive, the heterogeneous microstructure of the lithium-copper alloy that obtains is even, and is tiny, densification.
Concrete enforcement 19: the method for galvanic deposit lithium-copper alloy realizes by following steps in the present embodiment ion liquid system: one, with LiBF
4, Cu (BF
4)
2, the additive butynediol adds ionic liquid 1-butyl 3-methyl imidazolium tetrafluoroborate (BMIMBF successively
4) in, stirring and dissolving gets electrolytic solution, wherein LiBF
4Concentration be 150g/L, Cu (BF
4)
2Concentration be that 180g/L, additive account for 0.5% of electrolytic solution total mass; Two, electrolytic copper foil is carried out the galvanic deposit pre-treatment after, electrolytic copper foil is immersed in the electrolytic solution as negative electrode, and then copper sheet immersed in the electrolytic solution as anode, adopt the continuous current mode to carry out galvanic deposit 120min, use ethanol, washed with de-ionized water successively after then electrolytic copper foil being taken out, promptly get lithium-copper alloy; Wherein, control current density is 5A/m in the step 1
2, cathode and anode spacing is 2cm, keeps electrolyte temperature at 30 ℃; Step 1 and step 2 are carried out in being full of the glove box of argon gas.
The galvanic deposit pre-treatment is followed successively by conventional alkaline degreasing and (is containing sodium hydroxide 80gL in the present embodiment step 2
-1, yellow soda ash 30gL
-1, sodium phosphate 60gL
-1, water glass 10/gL
-1Degreasing fluid in oil removing 10min, the degreasing fluid temperature is 90 ℃), the 20%HCl solution acid pickling, washing then, dry again.
The thickness that present embodiment obtains lithium-copper alloy coating is about 8.4 μ m, coating evenly, have metalluster, the atomic percentage conc of Li is 29.6% (quality) in plasma emission spectrometer (ICP) the test result coating.
Concrete enforcement 20: the method for galvanic deposit lithium-copper alloy realizes by following steps in the present embodiment ion liquid system: one, with LiBF
4, Cu (BF
4)
2, the additive butynediol adds ionic liquid 1-butyl 3-methyl imidazolium tetrafluoroborate (BMIMBF successively
4) in, stirring and dissolving gets electrolytic solution, wherein LiBF
4Concentration be 100g/L, Cu (BF
4)
2Concentration be that 140g/L, additive account for 0.5% of electrolytic solution total mass; Two, electrolytic copper foil is carried out the galvanic deposit pre-treatment after, electrolytic copper foil is immersed in the electrolytic solution as negative electrode, and then copper sheet immersed in the electrolytic solution as anode, adopt the continuous current mode to carry out galvanic deposit 80min, use ethanol, washed with de-ionized water successively after then electrolytic copper foil being taken out, promptly get lithium-copper alloy; Wherein, control current density is 8A/m in the step 1
2, cathode and anode spacing is 3cm, keeps electrolyte temperature at 20 ℃; Step 1 and step 2 are carried out in being full of the glove box of argon gas.
The galvanic deposit pre-treatment is followed successively by conventional alkaline degreasing and (is containing sodium hydroxide 80gL in the present embodiment step 2
-1, yellow soda ash 30gL
-1, sodium phosphate 60gL
-1, water glass 10/gL
-1Degreasing fluid in oil removing 10min, the degreasing fluid temperature is 90 ℃), the 20%HCl solution acid pickling, washing then, dry again.
The thickness that present embodiment obtains lithium-copper alloy coating is about 6.3 μ m, coating evenly, have metalluster, the atomic percentage conc of Li is 15.7% (quality) in plasma emission spectrometer (ICP) the test result coating.
Claims (10)
1. the method for galvanic deposit lithium-copper alloy in the ion liquid system is characterized in that the method for galvanic deposit lithium-copper alloy in the ion liquid system realizes by following steps: one, with LiBF
4, Cu (BF
4)
2Add successively in the ionic liquid 1-butyl 3-methyl imidazolium tetrafluoroborate with additive, stirring and dissolving gets electrolytic solution, wherein the concentration of LiBF4 is 40～160g/L, the concentration of Cu (BF4) 2 is that 100～200g/L, additive account for 0.5%～2% of electrolytic solution total mass, and described additive is a butynediol; Two, after the anticathode material carries out the galvanic deposit pre-treatment, cathode material and anode material are immersed in the electrolytic solution simultaneously, adopt the continuous current mode to carry out galvanic deposit 10～120min, promptly obtain lithium-copper alloy on the cathode material surface; Wherein, control current density is 5～10A/m in the step 2
2, cathode material is copper, nickel, titanium or stainless steel, anode material is copper, platinum or graphite, keeps electrolyte temperature at 20～50 ℃; Step 1 and step 2 are all carried out in being full of the glove box of rare gas element.
2. the method for galvanic deposit lithium-copper alloy is characterized in that LiBF in the step 1 in a kind of ion liquid system according to claim 1
4Concentration be 80～120g/L.
3. the method for galvanic deposit lithium-copper alloy is characterized in that LiBF in the step 1 in a kind of ion liquid system according to claim 1
4Concentration be 100g/L.
4. according to the method for galvanic deposit lithium-copper alloy in claim 1, the 2 or 3 described a kind of ion liquid systems, it is characterized in that Cu (BF in the step 1
4)
2Concentration be 120～180g/L.
5. according to the method for galvanic deposit lithium-copper alloy in claim 1, the 2 or 3 described a kind of ion liquid systems, it is characterized in that Cu (BF in the step 1
4)
2Concentration be 150g/L.
6. the method for galvanic deposit lithium-copper alloy in a kind of ion liquid system according to claim 4 is characterized in that additive accounts for 0.8%～1.5% of electrolytic solution total mass in the step 1.
7. the method for galvanic deposit lithium-copper alloy in a kind of ion liquid system according to claim 4 is characterized in that additive accounts for 1% of electrolytic solution total mass in the step 1.
8. according to the method for galvanic deposit lithium-copper alloy in claim 1,2,3, the 6 or 7 described a kind of ion liquid systems, it is characterized in that adopting in the step 2 continuous current mode to carry out galvanic deposit 30～80min.
9. the method for galvanic deposit lithium-copper alloy in a kind of ion liquid system according to claim 8 is characterized in that control current density is 6～9A/m in the step 2
2
10. the method for galvanic deposit lithium-copper alloy in a kind of ion liquid system according to claim 8 is characterized in that control current density is 8A/m in the step 2
2
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912384A (en) * | 2012-10-31 | 2013-02-06 | 南京工业大学 | Method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy |
| CN109837561A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of metallic lithium powder and its electrochemical preparation method |
| CN114171713A (en) * | 2021-11-30 | 2022-03-11 | 淄博火炬能源有限责任公司 | Modified graphite cathode and preparation method thereof |
| CN114196996A (en) * | 2021-11-30 | 2022-03-18 | 淄博火炬能源有限责任公司 | LiCu/graphite composite pole piece and method for preparing LiCu/graphite composite pole piece through ionic liquid electrodeposition |
| CN114540886A (en) * | 2022-02-15 | 2022-05-27 | 中国石油大学(北京) | Method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition |
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2010
- 2010-02-08 CN CN201010301352A patent/CN101831677A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912384A (en) * | 2012-10-31 | 2013-02-06 | 南京工业大学 | Method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy |
| CN102912384B (en) * | 2012-10-31 | 2015-03-04 | 南京工业大学 | Method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy |
| CN109837561A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of metallic lithium powder and its electrochemical preparation method |
| CN114171713A (en) * | 2021-11-30 | 2022-03-11 | 淄博火炬能源有限责任公司 | Modified graphite cathode and preparation method thereof |
| CN114196996A (en) * | 2021-11-30 | 2022-03-18 | 淄博火炬能源有限责任公司 | LiCu/graphite composite pole piece and method for preparing LiCu/graphite composite pole piece through ionic liquid electrodeposition |
| CN114196996B (en) * | 2021-11-30 | 2023-09-15 | 淄博火炬能源有限责任公司 | LiCu/graphite composite pole piece and method for preparing LiCu/graphite composite pole piece by ionic liquid electrodeposition |
| CN114171713B (en) * | 2021-11-30 | 2023-09-15 | 淄博火炬能源有限责任公司 | Modified graphite negative electrode and preparation method thereof |
| CN114540886A (en) * | 2022-02-15 | 2022-05-27 | 中国石油大学(北京) | Method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition |
| CN114540886B (en) * | 2022-02-15 | 2022-12-27 | 中国石油大学(北京) | Method for preparing copper foil based on copper-containing composite ionic liquid electrodeposition |
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