CN103094524A - Tin alloy membrane electrode and application thereof - Google Patents
Tin alloy membrane electrode and application thereof Download PDFInfo
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- CN103094524A CN103094524A CN2012105946379A CN201210594637A CN103094524A CN 103094524 A CN103094524 A CN 103094524A CN 2012105946379 A CN2012105946379 A CN 2012105946379A CN 201210594637 A CN201210594637 A CN 201210594637A CN 103094524 A CN103094524 A CN 103094524A
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Abstract
The invention discloses a tin alloy membrane electrode and an application thereof. The tin alloy membrane electrode is prepared by the following steps: (1) preparing chemical plating solution by using thiourea, citric acid, sodium hypophosphite, concentrated sulfuric acid, stannous sulfate, nitrate of metal M and water, wherein the metal M is Ag, Fe, Ni, Co, Zn, Al, Mg or Cu; a pH (Potential Of Hydrogen) value of the chemical plating solution is in a range of 0.8-1.1, the concentration of the thiourea is 40-200g/L, the concentration of the citric acid is 20-80g/L, the concentration of the sodium hypophosphite is 30-160g/L, the concentration of the stannous sulfate is 0.1-0.4mol/L, and the concentration of the nitrate of the metal M is 0.1-1g/L; (2) corroding a copper foil by using sulfuric acid with the concentration of 0.3-0.6mol/L for 10-15 minutes, and then washing and drying by distilled water; and (3) placing the corroded copper foil in the chemical plating solution with the temperature kept within a range of 30-40 DEG C, and reacting for 30-120s; forming a tin alloy membrane on the surface of the copper foil; and drying to obtain the tin alloy membrane electrode. The invention further provides an application of the tin alloy membrane electrode as a cathode of a lithium ion battery, and has the advantages of high capacity and stable properties.
Description
(1) technical field
The present invention relates to a kind of tin alloy film electrode with and as the application of lithium ion battery negative.
(2) background technology
Along with the increase day by day of people's environmental consciousness, the use of the toxic metals such as lead, cadmium is restricted day by day, and in addition, along with the develop rapidly of industrial technology and electronics technology, people are to high power capacity, and the chemical power source demand of small size constantly increases.Therefore need to seek the green secondary cell of high power capacity of new replaced traditional lead acid batteries and nickel-cadmium cell.Lithium ion battery becomes one of strong candidate naturally.
Since nineteen ninety lithium ion battery commercialization, extensive must being applied in electronic product, in order to satisfy the development of pure electric automobile and hybrid-electric car, must seek new negative material.But present commercial lithium ion battery negative mainly adopts graphite material.The carbon negative pole material good cycling stability, but its lithium storage content is lower, theoretical specific capacity is low, is only 372mAh/g, and in the first charge-discharge process, electrolyte decomposes and can form passivating film at carbon surface.And the deposition potential of carbon negative pole material embedding lithium current potential and lithium metal is close, and in battery charge and discharge process, carbon electrodes is easily separated out Li dendrite, thereby causes battery short circuit and a series of safety problems such as blast.
The development need in epoch is the Portable power source of high power capacity more, and for solving the low problem of negative material capacity, the researcher is the metal of target diversion high power capacity (as Sn, Si, Sb etc.) and compound thereof.Pure Sn has very high reactivity to lithium electrode, and it can form alloy with 4.4 lithium atoms in theory, and this makes tin have quite high reversible electrode capacity (990mAh/g), has showed wide Research Prospects for tin-based material is used for lithium ion battery.But metallic tin produces serious Volumetric expansion (up to 300%) in the removal lithium embedded process, this effect can cause the electrode material powdered, reduces cycle life.
In order to cushion the change in volume of tin electrode, researchers adopt different preparation methods to study pure Sn film, Sn/C laminated film, the various tin base cathode materials such as Sn-Ni alloy, result shows that the chemical property of these materials has had larger improvement, but still is difficult to satisfy practical requirement.Therefore, the reaction mechanism of tin base cathode material and experimental technique remain further to be studied.
The tinbase thin-film material substantially all adopts magnetron sputtering to prepare in experiment in the past, and this method power consumption is large, and complex process is unfavorable for industrialization.Chemical plating is different from plating, and it is impressed current not, the metal deposition process that carries out through controlling chemical reduction method under the catalytic action of metal surface.Like this can not only energy savings, and chemical plating fluid is stable, can realize that large-scale industrialization produces continuously.
(3) summary of the invention
The primary technical problem that the present invention will solve is to provide a kind of tin alloy film electrode with three-dimensional foam structure, its negative material as lithium ion battery has advantages of that capacity is high, stable performance, and this tin alloy film electrode preparation method technique is simple, pattern is easily controlled.
Second technical problem that the present invention will solve is to provide described tin alloy film electrode as the application of lithium ion battery negative.
Lower mask body is introduced technical scheme of the present invention.
The invention provides a kind of tin alloy film electrode, its preparation comprises the following steps:
(1) prepare chemical plating fluid with nitrate and the water of thiocarbamide, citric acid, inferior sodium phosphate, the concentrated sulfuric acid, stannous sulfate, metal M, metal M is Ag, Fe, Ni, Co, Zn, Al, Mg or Cu, the pH of described chemical plating fluid is 0.8 ~ 1.1, wherein: thiourea concentration is 40 ~ 200g/L, citric acid concentration is 20 ~ 80g/L, the ortho phosphorous acid na concn is 30 ~ 160g/L, and stannous sulfate concentration is 0.1 ~ 0.4mol/L, and the nitrate concentration of metal M is 0.1 ~ 1g/L;
(2) Copper Foil is used 0.3-0.6mol/L sulfuric acid corrosion 10-15min, then with distilled water washing, drying;
(3) Copper Foil after corroding is put into the chemical plating fluid that temperature remains on 30 ~ 40 ℃ and is reacted 30 ~ 120s, forms tin alloy film at copper foil surface, and drying obtains the tin alloy film electrode.
In the present invention, M is preferably Ag, Fe, Ni or Co; Most preferably M is Ag.
In the present invention, in the described chemical plating fluid of step (1), add the concentrated sulfuric acid in order to the pH that controls chemical plating fluid in 0.8 ~ 1.1.
In the present invention, in described chemical plating fluid, thiourea concentration is preferably 40 ~ 120g/L, most preferably is 40g/L; Citric acid concentration is preferably 30 ~ 60 g/L, most preferably is 40 g/L; The ortho phosphorous acid na concn is preferably 60 ~ 100 g/L, most preferably is 80 g/L; Stannous sulfate concentration is preferably 0.2 ~ 0.4mol/L, most preferably is 0.3mol/L; The nitrate concentration of M metal is preferably 0.2-0.8 g/L, most preferably is 0.6g/L.
Step of the present invention (2) is used the sulfuric acid treatment Copper Foil, becomes a concavo-convex not all right matsurface through the sulfuric acid treatment copper foil surface by shiny surface, is conducive to form the three-dimensional foam structure when chemical plating stannum.Enormousness when tin thin film three-dimensional foam structure can effectively be alleviated the tin removal lithium embedded expands and has greatly improved the cycle performance of battery, and three-dimensional structure has improved tin and reduced the path of removal lithium embedded with the contact area of electrolyte simultaneously, has improved the high rate capability of battery.
In the present invention, the reaction time in described step (3) is preferably 60s.
Further, the present invention specifically recommends the preparation of described tin alloy film electrode to carry out in accordance with the following steps:
(1) prepare chemical plating fluid with nitrate and the water of thiocarbamide, citric acid, inferior sodium phosphate, the concentrated sulfuric acid, stannous sulfate, metal M, the pH of described chemical plating fluid is 0.8 ~ 1.1, wherein: thiourea concentration is 40 ~ 200g/L, citric acid concentration is 20 ~ 80g/L, the ortho phosphorous acid na concn is 30 ~ 160g/L, stannous sulfate concentration is 0.1 ~ 0.4mol/L, and the nitrate concentration of metal M is 0.1 ~ 1g/L;
(2) Copper Foil is used 0.3-0.6 mol/L sulfuric acid corrosion 10-15min, then with distilled water washing, drying;
(3) Copper Foil after corroding is put into the chemical plating fluid that temperature remains on 30 ~ 40 ℃ and is reacted 30 ~ 120s, and drying obtains the tin alloy film electrode.
Further, the preparation of the preferred described tin alloy film electrode of the present invention is carried out in accordance with the following steps:
(1) with thiocarbamide, citric acid, inferior sodium phosphate, the concentrated sulfuric acid, stannous sulfate, silver nitrate and water preparation chemical plating fluid, the pH of described chemical plating fluid is 0.8 ~ 1.1, wherein: thiourea concentration is 40 g/L, citric acid concentration is 40 g/L, sodium phosphite concentration is 80 g/L, stannous sulfate concentration is 0.3 mol/L, and silver nitrate concentration is 0.6g/L;
(2) with Copper Foil with 0.5 mol/L sulfuric acid corrosion 10min, then with distilled water washing, drying;
(3) Copper Foil after corroding is put into the chemical plating fluid that temperature remains on 30 ~ 40 ℃ and is reacted 60s, and drying obtains the tin alloy film electrode.
The present invention also provides the application of described tin alloy film electrode as lithium ion battery negative, has advantages of that capacity is high, stable performance.
compared with prior art, beneficial effect of the present invention is: the present invention adopts method zinc-plated alloy on the Copper Foil of processing through sulfuric acid corrosion of chemical plating, prepare the tin alloy film of three-dimensional foam structure, (the copper metal can not removal lithium embedded be inertia with respect to lithium not only to have introduced inert element, the buffering medium of their volumetric expansions during as the tin removal lithium embedded), and have firmly that more effective the preventing of three-dimensional foam structure causes electrode powder because of volumetric expansion, effectively improved the cyclical stability of battery, make it to have capacity high, the advantage of stable performance, and preparation technology is simple, film morphology is easily controlled.
(4) description of drawings
Fig. 1-1-1 is the SEM figure of the sn-ag alloy thin-film material that makes of embodiment 1.
Fig. 1-1-2 is the XRD figure of the sn-ag alloy thin-film material that makes of embodiment 1.
Fig. 2-1-1 is the SEM figure of the tin ferroalloy thin-film material that makes of embodiment 2.
Fig. 2-1-2 is the XRD figure of the tin ferroalloy thin-film material that makes of embodiment 2.
Fig. 3-1-1 is the SEM figure of the tin-nickel alloy thin-film material that makes of embodiment 3.
Fig. 3-1-2 is the XRD figure of the tin-nickel alloy thin-film material that makes of embodiment 3.
Fig. 4-1-1 is the SEM figure of the tin-cobalt alloy thin-film material that makes of embodiment 4.
Fig. 4-1-2 is the XRD figure of the tin-cobalt alloy thin-film material that makes of embodiment 4.
(5) embodiment
The below is described further technical scheme of the present invention with specific embodiment, but protection scope of the present invention is not limited to this:
Embodiment 1-1
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.03mol stannous sulfate, the 0.06g silver nitrate is heated to 30-40 ℃ with plating solution.With 1cm
2Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, and is then dry with distilled water washing final vacuum, puts it in plating solution, and the reaction time is 60s, and drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
The sn-ag alloy thin-film material that obtains is carried out scanning electron microscopy detect, result is as shown in Fig. 1-1-1, and result shows: the sn-ag alloy film of preparation has the three-dimensional foam structure.
The sn-ag alloy thin-film material that makes is scraped from Copper Foil, carry out the test of X-ray powder diffraction, result is as shown in Fig. 1-1-2, and result shows: chemical plating is plated in tin silver film on Copper Foil effectively.
Embodiment 1-2
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.02mol stannous sulfate, the 0.04g silver nitrate is heated to 30-40 ℃ with plating solution.With 1cm
2Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, and is then dry with distilled water washing final vacuum, puts it in plating solution, and the reaction time is 60s, and drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
Embodiment 1-3
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.04mol stannous sulfate, the 0.08g silver nitrate is heated to 30-40 ℃ with plating solution.With 1cm
2Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, and is then dry with distilled water washing final vacuum, puts it in plating solution, and the reaction time is 60s, and drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
Embodiment 2-1
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.03mol stannous sulfate, the 0.06g ferric nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 60s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
The tin ferroalloy thin-film material that obtains is carried out scanning electron microscopy detect, result is as shown in Fig. 2-1-1, and result shows: the tin ferroalloy film of preparation has the three-dimensional foam structure.
The tin ferroalloy thin-film material that makes is scraped from Copper Foil, carry out the test of X-ray powder diffraction, result is as shown in Fig. 2-1-2, and result shows: chemical plating is plated in the tin iron thin film on Copper Foil effectively.
Embodiment 2-2
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.02mol stannous sulfate, the 0.04g ferric nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 60s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
Embodiment 2-3
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.04mol stannous sulfate, the 0.08g ferric nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 60s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
Embodiment 3-1
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.03mol stannous sulfate, the 0.06g nickel nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 90s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
The tin-nickel alloy thin-film material that obtains is carried out scanning electron microscopy detect, result is as shown in Fig. 3-1-1, and result shows: the tin-nickel alloy film of preparation has the three-dimensional foam structure.
The tin-nickel alloy thin-film material that makes is scraped from Copper Foil, carry out the test of X-ray powder diffraction, result is as shown in Fig. 3-1-2, and result shows: chemical plating is plated in tin nickel film on Copper Foil effectively.
Embodiment 3-2
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.02mol stannous sulfate, the 0.04g nickel nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 90s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
Embodiment 3-3
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.04mol stannous sulfate, the 0.08g nickel nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 90s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
Embodiment 4-1
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.03mol stannous sulfate, the 0.06g cobalt nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 60s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
The tin-cobalt alloy thin-film material that obtains is carried out scanning electron microscopy detect, result is as shown in Fig. 4-1-1, and result shows: the tin-cobalt alloy film of preparation has the three-dimensional foam structure.
The tin-cobalt alloy thin-film material that makes is scraped from Copper Foil, carry out the test of X-ray powder diffraction, result is as shown in Fig. 4-1-2, and result shows: chemical plating is plated in the tin cobalt thin film on Copper Foil effectively.
Embodiment 4-2
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.02mol stannous sulfate, the 0.04g cobalt nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 60s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
Embodiment 4-3
100ml distilled water is joined drip concentrated sulfuric acid control plating solution pH in the 250ml beaker 1.0, add successively the 4g citric acid, the 8g inferior sodium phosphate, the 4g thiocarbamide, the 0.04mol stannous sulfate, the 0.08g cobalt nitrate is heated to 30-40 ℃ with plating solution.Copper Foil is with 0.5 mol/L sulfuric acid corrosion 10min, then dry with distilled water washing final vacuum, put it in plating solution, the reaction time is 60s, drying obtains product.
Test battery is comprised of tin thin film negative pole, metal lithium sheet and the PP/PE/PP of Asahi Chemical Industry type barrier film, and electrolyte is 1 mol/L LiPF6/ (m (EC): m (DMC)=1: 1). be assembled into 2032 type button half-cells under argon gas being full of.Electro-chemical test carries out on Land battery test system (CT 2001A), and voltage range is at 0.01～1.5 V, and current density is at 0.1mA/cm
2
The chemical property of the sn-ag alloy thin-film electrode material for preparing under the synthesis condition of form 1 embodiment 1-1～1-3.
The chemical property of the tin ferroalloy thin-film electrode material for preparing under the synthesis condition of form 2 embodiment 2-1～2-3.
The chemical property of the tin-nickel alloy thin-film electrode material for preparing under the synthesis condition of form 3 embodiment 3-1～3-3.
The chemical property of the tin-cobalt alloy film electrode material for preparing under the synthesis condition of form 4 embodiment 4-1～4-3.
Claims (10)
1. tin alloy film electrode, its preparation comprises the following steps:
(1) prepare chemical plating fluid with nitrate and the water of thiocarbamide, citric acid, inferior sodium phosphate, the concentrated sulfuric acid, stannous sulfate, metal M, metal M is Ag, Fe, Ni, Co, Zn, Al, Mg or Cu, the pH of described chemical plating fluid is 0.8 ~ 1.1, wherein: thiourea concentration is 40 ~ 200g/L, citric acid concentration is 20 ~ 80g/L, the ortho phosphorous acid na concn is 30 ~ 160g/L, and stannous sulfate concentration is 0.1 ~ 0.4mol/L, and the nitrate concentration of metal M is 0.1 ~ 1g/L;
(2) Copper Foil is used 0.3-0.6mol/L sulfuric acid corrosion 10-15min, then with distilled water washing, drying;
(3) Copper Foil after corroding is put into the chemical plating fluid that temperature remains on 30 ~ 40 ℃ and is reacted 30 ~ 120s, forms tin alloy film at copper foil surface, and drying obtains the tin alloy film electrode.
2. tin alloy film electrode as claimed in claim 1, it is characterized in that: M is Ag, Fe or Ni.
3. tin alloy film electrode as claimed in claim 1, it is characterized in that: M is Ag.
4. tin alloy film electrode as described in one of claim 1 ~ 3, it is characterized in that: in described chemical plating fluid, thiourea concentration is 40 ~ 120g/L, citric acid concentration is 30 ~ 60 g/L, the ortho phosphorous acid na concn is 60 ~ 100 g/L, stannous sulfate concentration is 0.2 ~ 0.4mol/L, and the nitrate concentration of M metal is 0.2-0.8 g/L.
5. tin alloy film electrode as claimed in claim 4, it is characterized in that: in described chemical plating fluid, thiourea concentration is 40 g/L, citric acid concentration is 40 g/L, the ortho phosphorous acid na concn is 80 g/L, and stannous sulfate concentration is 0.3 mol/L, and the nitrate concentration of metal M is 0.6g/L.
6. tin alloy film electrode as described in one of claim 1 ~ 3, it is characterized in that: in described step (3), the reaction time is 60s.
7. tin alloy film electrode as described in one of claim 1 ~ 3 is characterized in that the preparation of described tin alloy film electrode is carried out in accordance with the following steps:
(1) prepare chemical plating fluid with nitrate and the water of thiocarbamide, citric acid, inferior sodium phosphate, the concentrated sulfuric acid, stannous sulfate, metal M, the pH of described chemical plating fluid is 0.8 ~ 1.1, wherein: thiourea concentration is 40 ~ 200g/L, citric acid concentration is 20 ~ 80g/L, the ortho phosphorous acid na concn is 30 ~ 160g/L, stannous sulfate concentration is 0.1 ~ 0.4mol/L, and the nitrate concentration of metal M is 0.1 ~ 1g/L;
(2) Copper Foil is used 0.3-0.6 mol/L sulfuric acid corrosion 10-15min, then with distilled water washing, drying;
(3) Copper Foil after corroding is put into the chemical plating fluid that temperature remains on 30 ~ 40 ℃ and is reacted 30 ~ 120s, and drying obtains the tin alloy film electrode.
8. tin alloy film electrode as claimed in claim 7, it is characterized in that in described chemical plating fluid, thiourea concentration is 40 ~ 120g/L, citric acid concentration is 30 ~ 60 g/L, the ortho phosphorous acid na concn is 60 ~ 100 g/L, stannous sulfate concentration is 0.2 ~ 0.4mol/L, and the nitrate concentration of M metal is 0.2-0.8 g/L.
9. tin alloy film electrode as claimed in claim 8 is characterized in that the preparation of described tin alloy film electrode is carried out in accordance with the following steps:
(1) with thiocarbamide, citric acid, inferior sodium phosphate, the concentrated sulfuric acid, stannous sulfate, silver nitrate and water preparation chemical plating fluid, the pH of described chemical plating fluid is 0.8 ~ 1.1, wherein: thiourea concentration is 100 g/L, citric acid concentration is 40 g/L, sodium phosphite concentration is 80 g/L, stannous sulfate concentration is 0.3 mol/L, and silver nitrate concentration is 0.6g/L;
(2) with Copper Foil with 0.5 mol/L sulfuric acid corrosion 10min, then with distilled water washing, drying;
(3) Copper Foil after corroding is put into the chemical plating fluid that temperature remains on 30 ~ 40 ℃ and is reacted 60s, and drying obtains the tin alloy film electrode.
10. tin alloy film electrode as claimed in claim 1 is as the application of lithium ion battery negative.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594637.9A CN103094524B (en) | 2012-12-31 | 2012-12-31 | A kind of tin alloy membrane electrode and application thereof |
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| CN105483777A (en) * | 2016-02-19 | 2016-04-13 | 苏州市华婷特种电镀有限公司 | Electroplating liquid for obtaining platinum plating |
| WO2016080823A1 (en) * | 2014-11-19 | 2016-05-26 | Ontiveros Balcázar Alberto Manuel | Parts and electrodes made of zinc, coated in tin, and method for the production thereof |
| CN105679997A (en) * | 2016-01-27 | 2016-06-15 | 柳州豪祥特科技有限公司 | Method for manufacturing tin-copper alloy pole piece through electrolytic process |
| CN110565078A (en) * | 2019-07-11 | 2019-12-13 | 中国科学院兰州化学物理研究所 | Method for preparing cobalt-sulfur film on copper surface based on reverse replacement |
| CN112615057A (en) * | 2020-12-15 | 2021-04-06 | 广东微电新能源有限公司 | Preparation method of solid-state lithium ion battery and solid-state lithium ion battery |
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| CN105679997A (en) * | 2016-01-27 | 2016-06-15 | 柳州豪祥特科技有限公司 | Method for manufacturing tin-copper alloy pole piece through electrolytic process |
| CN105483777A (en) * | 2016-02-19 | 2016-04-13 | 苏州市华婷特种电镀有限公司 | Electroplating liquid for obtaining platinum plating |
| CN110565078A (en) * | 2019-07-11 | 2019-12-13 | 中国科学院兰州化学物理研究所 | Method for preparing cobalt-sulfur film on copper surface based on reverse replacement |
| CN112615057A (en) * | 2020-12-15 | 2021-04-06 | 广东微电新能源有限公司 | Preparation method of solid-state lithium ion battery and solid-state lithium ion battery |
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| CN103094524B (en) | 2015-10-07 |
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