CN101275256B - Method for preparing metal, alloy, metallic oxide and alloy oxide composite power by epitaxial cathode electrochemical codeposition technology - Google Patents
Method for preparing metal, alloy, metallic oxide and alloy oxide composite power by epitaxial cathode electrochemical codeposition technology Download PDFInfo
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Abstract
The invention provides a method for preparing metal alloy, metal oxidant and alloy oxidant compound powder by using extension cathode electrochemistry co-deposition technology. The method uses an extension cathode way, under the condition of co-deposition, to continuous blend the electrolyte to dynamically contact carbon particle even-distributed in the solution to the cathode again and again to become the extension carbon particle cathode; the outer surface continuously deposits the metal or alloy to obtain the compound powder with the cover C of the metal or alloy. The cover C of the metal or alloy can obtain the compound powder with the cover C metal oxidant or alloy oxidant via the thermal treatment. The preparation technique is stable and the operation is simple. The invention can easily obtain the metal or alloy or metal oxidant or alloy oxidant covering carbon particle with different sizes film thickness; the size of the particle is even and the cost performance of the product is high.
Description
Technical field
The present invention relates to a kind of electrode materials, specifically, be meant a kind of extension negative electrode mode that adopts, under the condition of electrochemical co-deposition, constantly stir electrolytic solution, make that equally distributed carbon particles dynamically contacts repeatedly with negative electrode in the solution, become the extension negative electrode, at continuous metal refining of its carbon particles outside surface or alloy, obtained metal or alloy and coated the C composite powder.Can also carry out follow-up thermal treatment, obtain metal oxide and alloyed oxide and coat the C composite powder.
Background technology
As electrode materials, its preparation method has ball milled, evaporation-coacervation, spray heating decomposition, plasma technique, laser technology etc. with the metal or alloy of doping carbon.The Prepared by Ball Milling time is long, and it is very difficult to obtain nano-scale level particle; Evaporation-coacervation can make high purity in theory, is uniformly dispersed, particle diameter is little, the nanometer ultra micron of cleaning surfaces, but in the actual production, because the preparation condition harshness is difficult to produce nano-grade size alloy carbon coated particle.Plasma technique and laser technology are limited by the equipment sample chamber size, and preparation electrode materials price is very high, is difficult to use in actual production.
The method that the electrochemical co-deposition technology prepares metal, alloy, metal oxide and alloyed oxide composite powder is to adopt a kind of extension negative electrode mode, adding nano-micrometre level carbon particles in all kinds of metal-salts and conducting salt are the aqueous solution of solute is deposit solution, under the condition of electrochemical co-deposition, constantly stir electrolytic solution, make that equally distributed carbon particles dynamically contacts repeatedly with negative electrode in the solution, become the carbon particles negative electrode of extension, at continuous metal refining of its outside surface or alloy, can obtain metal or alloy and coat the C composite nano powder; Heat-treat follow-up, can obtain the composite powder that metal oxide and alloyed oxide coat C.The advantage of this method is to obtain by the kind of the kind of control solution component, complexing agent, additive and parameters such as electric current, current potential size metal or alloy or the metal oxide and the alloyed oxide carbon coated composite powder of different size thickness, the sub-size of this powder is even, its stable preparation process, easy and simple to handle, product price ratio height.
Summary of the invention
The objective of the invention is to have proposed a kind of extension negative electrode mode, in being the aqueous solution of solute, all kinds of metal-salts and conducting salt and additive add nanometer and a micron carbon particles is a deposit solution, under the condition of electrochemical co-deposition, constantly stir electrolytic solution, make that equally distributed carbon particles dynamically contacts repeatedly with negative electrode in the solution, become the carbon particles negative electrode of extension,, obtained the method for metal or alloy coating C composite powder at continuous metal refining of its outside surface or alloy.The metal or alloy that the present invention obtains can get metal oxide or alloyed oxide carbon coated composite particles through aftertreatment.
A kind of power by epitaxial cathode electrochemical codeposition technology of the present invention prepares the method for metal, alloy, metal oxide and alloyed oxide composite powder, and its step is as follows:
The first step:
At first prepare electrolytic solution one:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is EDTA (disodium EDTA) or citric acid and salt or pyrophosphate salt, and concentration is at 0.01～5mol/L;
3. the solution that 1 step is prepared is slowly poured in the solution that 2 steps prepare;
4. a certain amount of graphite or carbon black or other carbon particles are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
5. the solution that 4 steps are prepared is slowly poured in the solution that 3 steps prepare, and it is carried out ultrasonic concussion 30-120 minute can be stand-by.
Preparation electrolytic solution two:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt or sulfuric acid Cobalt or nitric acid Cobalt, and concentration is at 0.01～5mol/L;
3. solvent is distilled water or deionized water, and solute is EDTA (disodium EDTA) or citric acid and salt or pyrophosphate salt, and concentration is at 0.01～5mol/L;
4. a certain amount of graphite or carbon black or other carbon particles are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
5. the solution that 1 step and 2 steps are prepared is slowly poured in the solution that 3 steps prepare;
6. the solution that 4 steps are prepared is slowly poured in the solution that 5 steps prepare, and it is carried out ultrasonic concussion 30-120 minute can be stand-by.
Preparation electrolytic solution three:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt or sulfuric acid Cobalt or nitric acid Cobalt, and concentration is at 0.01～5mol/L;
3. solvent is distilled water or deionized water, and solute is a Sunmorl N 60S, and solute concentration is respectively at 0.01～5mol/L;
4. solvent is distilled water or deionized water, and solute is a citric acid, and solute concentration is respectively at 0.01～5mol/L;
5. a certain amount of graphite or carbon black or other carbon particles are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
6. the solution that 1 step is prepared is slowly poured in the solution that 3 steps prepare;
7. the solution that 2 steps are prepared is slowly poured in the solution that 4 steps prepare;
8. 6,7 steps ground solution was mixed in 1: 1 in molar ratio～1: 10 or 1: 10～1: 1;
9. the solution that 5 steps are prepared is slowly poured in the solution that 8 steps prepare in required ratio, and it is carried out ultrasonic concussion 30-120 minute can be stand-by.
Second step: the electrolytic solution that the first step configures is put into plating tank, and anode and cathode is provided with respectively as shown in Figure 1, and alr mode can adopt mechanical type to stir pawl (a) and (b) or magnetic stir bar (c).Consider that the effect that utilizes gravity is easy to the carbon particles negative electrode that obtains to extend, so negative electrode is a sheet, is positioned over bottom land.Anode can adopt the disk shape among the left figure, also can adopt the strip among the right figure, places the top respectively.
The 3rd step: galvanic deposit
Connect circuit and carry out galvanic deposit according to calculating the size of current energising.The galvanic deposit electric current is 1～10A/dm
2(ampere/square decimeter), tank liquor temperature are 20～60 ℃, and electrodeposition time is 1～300 minute, and deposition process stirs with the little speed of agitator.
The 4th step: centrifugation powder
Adopt centrifugal method to separate powder, reaction soln and the good carbon dust of plating are put into together the test tube of whizzer.It is 500-6000 rev/min that centrifuge speed adopts rotating speed, and each centrifugation time is 1-30 minute.Can carry out centrifugal treating three～ten times (preceding spend several times ionized water rinsing, use the ethanol rinsing for the last time).
The 5th step: oven dry
The powder that the 4th step was obtained 100 ℃ of bakings 1 hour under vacuum condition are taken out stand-by.
The 6th step: thermal treatment
Needing acquisition metal oxide coating C powder or alloyed oxide to coat the C powder can heat-treat the powder in the 4th step under suitable oxidizing temperature.
The 7th step: the preparation of slip
The making of slurry: by weight for powder: styrene-butadiene rubber(SBR): thickening material: deionized water be the suitable ratio that requires with the powder of obtaining, styrene-butadiene rubber(SBR), thickening material and deionized water are modulated pulping in beaker.
The 8th step: the making of electrode
Slurry is spread upon on the uneven surface of collector.Wait to do the back and go out circular electrode with punching pin.
Use tabletting machine with the electrode compression moulding of preparation as positive pole, be negative pole with the lithium sheet, with the capillary polypropylene barrier film, electrolytic solution is 1M LiPF between positive pole and the negative pole
6/ EC+DMC (1: 1), M represents volumetric molar concentration.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt blue electric battery test system at room temperature to carry out the constant current charge-discharge test.
In the present invention, collector can be a kind of metal electrode of making or porous foam nickel, porous foam copper or the porous foam aluminium in nickel foil, aluminium foil, Copper Foil, graphite, carbon fiber, nickel plate or the platinized platinum.
In the present invention, metal and alloy can be various materials that can galvanic deposit such as tin, cobalt, iron, tungsten, nickel etc. and tin-cobalt, tin-iron, tin-tungsten tin-nickel.
In the present invention, metal oxide and alloyed oxide can be tin, cobalt, iron, tungsten, nickel etc. and tin-cobalt, tin-iron, tin-oxide compounds such as tungsten tin-nickel.
Advantage of the present invention: adopt a kind of extension negative electrode mode, make the bulk carbon particle under constantly stirring, dynamically contact repeatedly with carbon cathode, become the carbon particles negative electrode of extension, at continuous metal refining of its outside surface or alloy, obtained even metal or alloy and coated C particle composite powder, can get metal oxide or alloyed oxide carbon coated particle composite powder through aftertreatment.Its stable preparation process, easy and simple to handle, obtain metal or alloy or the metal oxide or the alloyed oxide carbon coated particle powder of different size thickness easily, size of particles is even, product price ratio height.
Description of drawings
Fig. 1 electric deposition device figure
Fig. 2 specific discharge capacity curve
Fig. 3 Sn-Co-C electrode charge and discharge specific storage and efficient
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
The present invention adopts a kind of extension negative electrode mode, makes the bulk carbon particle under constantly stirring, and dynamically contacts repeatedly with negative electrode, becomes the carbon particles negative electrode of extension, constantly deposits the Sn-Co alloy at its outside surface, has obtained uniform Sn-Co-C composite nano powder.Present method comprises the following steps:
The first step:
At first prepare electrolytic solution one:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is EDTA (disodium EDTA) or citric acid and salt or pyrophosphate salt, and concentration is at 0.01～5mol/L;
3. the solution that 1 step is prepared is slowly poured in the solution that 2 steps prepare;
4. a certain amount of graphite or carbon black or other carbon particles are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
5. the solution that 4 steps are prepared is slowly poured in the solution that 3 steps prepare, and it is carried out ultrasonic concussion 30-120 minute can be stand-by.
Preparation electrolytic solution two:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt or sulfuric acid Cobalt or nitric acid Cobalt, and concentration is at 0.01～5mol/L;
3. solvent is distilled water or deionized water, and solute is EDTA (disodium EDTA) or citric acid and salt or pyrophosphate salt, and concentration is at 0.01～5mol/L;
4. a certain amount of graphite or carbon black or other carbon particles are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
5. the solution that 1 step and 2 steps are prepared is slowly poured in the solution that 3 steps prepare;
6. the solution that 4 steps are prepared is slowly poured in the solution that 5 steps prepare, and it is carried out ultrasonic concussion 30-120 minute can be stand-by.
Preparation electrolytic solution three:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt or sulfuric acid Cobalt or nitric acid Cobalt, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt or sulfuric acid Cobalt or nitric acid Cobalt, and concentration is at 0.01～5mol/L;
3. solvent is distilled water or deionized water, and solute is a Sunmorl N 60S, and solute concentration is respectively at 0.01～5mol/L;
4. solvent is distilled water or deionized water, and solute is a citric acid, and solute concentration is respectively at 0.01～5mol/L;
5. a certain amount of graphite or carbon black or other carbon particles are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
6. the solution that 1 step is prepared is slowly poured in the solution that 3 steps prepare;
7. the solution that 2 steps are prepared is slowly poured in the solution that 4 steps prepare;
8. 6,7 steps ground solution was mixed in 1: 1 in molar ratio～1: 10 or 1: 10～1: 1;
9. the solution that 5 steps are prepared is slowly poured in the solution that 8 steps prepare in required ratio, and it is carried out ultrasonic concussion 30-120 minute can be stand-by.
Second step: the electrolytic solution that the first step configures is put into plating tank, and anode and cathode is provided with respectively as shown in Figure 1, and alr mode can adopt mechanical type to stir pawl (a) and (b) or magnetic stir bar (c).Consider that the effect that utilizes gravity is easy to the carbon particles negative electrode that obtains to extend, so negative electrode is a sheet, is positioned over bottom land.Anode can adopt the disk shape among the left figure, also can adopt the strip among the right figure, places the top respectively.
The 3rd step: galvanic deposit
Connect circuit and carry out galvanic deposit according to calculating the size of current energising.The galvanic deposit electric current is 1～10A/dm
2(ampere/square decimeter), tank liquor temperature are 20～60 ℃, and electrodeposition time is 1～300 minute, and deposition process stirs with the little speed of agitator.
The 4th step: centrifugation powder
Adopt centrifugal method to separate powder, reaction soln and the good carbon dust of plating are put into together the test tube of whizzer.It is 500-6000 rev/min that centrifuge speed adopts rotating speed, and each centrifugation time is 1-30 minute.Carry out centrifugal treating altogether three～ten times (preceding spend several times ionized water rinsing, use the ethanol rinsing for the last time).
The 5th step: oven dry
The powder that the 4th step was obtained 100 ℃ of bakings 1 hour under vacuum condition are taken out stand-by.
The 6th step: thermal treatment
Needing acquisition metal oxide coating C powder or alloyed oxide to coat the C powder can heat-treat the powder in the 4th step under suitable oxidizing temperature.
The 7th step: the preparation of slip
The making of slurry: by weight for powder: styrene-butadiene rubber(SBR): thickening material: deionized water be the suitable ratio that requires with the powder of obtaining, styrene-butadiene rubber(SBR), thickening material and deionized water are modulated pulping in beaker.
The 8th step: the making of electrode
Slurry is spread upon on the uneven surface of collector.Wait to do the back and go out circular electrode with punching pin.
Use tabletting machine with the electrode compression moulding of preparation as positive pole, be negative pole with the lithium sheet, with the capillary polypropylene barrier film, electrolytic solution is 1M LiPF between positive pole and the negative pole
6/ EC+DMC (1: 1), M represents volumetric molar concentration.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt blue electric battery test system at room temperature to carry out the constant current charge-discharge test.
In the present invention, collector can be a kind of metal electrode of making or porous foam nickel, porous foam copper or the porous foam aluminium in nickel foil, aluminium foil, Copper Foil, graphite, carbon fiber, nickel plate or the platinized platinum.
In the present invention, metal and alloy can be various materials that can galvanic deposit such as tin, cobalt, iron, tungsten, nickel etc. and tin-cobalt, tin-iron, tin-tungsten tin-nickel.
In the present invention, metal oxide and alloyed oxide can be tin, cobalt, iron, tungsten, nickel etc. and tin-cobalt, tin-iron, tin-oxide compounds such as tungsten tin-nickel.
(1), gets SnCl
4Concentration is 0.2mol/L, and citric acid concentration is 0.2mol/L, respectively after the dissolving, SnCl
4Solution is poured in the citric acid solution.
(2), the weight of C is to take by weighing at 1: 2 by the mol ratio of Sn and C, and it is slowly poured in the 1 step solution for preparing, it is carried out ultrasonic concussion 30 minutes can be stand-by.Adopt the room temperature galvanic deposit 1 hour in above solution of Fig. 1 a device, the galvanic deposit current density is 100mA/cm
2, magnetic agitation.Adopt centrifugal method separation of Sn-C powder, reaction soln and the good carbon dust of plating are put into together the test tube of whizzer.It is 2000r that centrifuge speed adopts rotating speed, and each centrifugation time is 3 minutes.Carry out centrifugal treating altogether ten times (preceding nine times use deionized water, use ethanol for the last time).The powder that obtains 100 ℃ of bakings 1 hour under vacuum condition are taken out stand-by.By weight for powder: styrene-butadiene rubber(SBR): thickening material: deionized water is 1000: 50: 14: 1400 ratio is the powder of obtaining, styrene-butadiene rubber(SBR), and thickening material and deionized water are modulated pulping in beaker.Powder is mixed well slurry with slurry by mass ratio at 1: 1.464, spreads upon on the uneven surface of collector.Wait to do the back and go out circular electrode with punching pin, the gained sample is called the 1# sample.
Use tabletting machine with the Sn carbon coated electrode compression moulding of preparation as positive pole, be negative pole with the lithium sheet, with the capillary polypropylene barrier film, electrolytic solution is 1M LiPF between positive pole and the negative pole
6/ EC+DMC (1: 1), M represents volumetric molar concentration.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt blue electric battery test system at room temperature to carry out the constant current charge-discharge test, the specific storage curve is seen the 1# sample of Fig. 2.
(1), gets SnCl
4Concentration is 0.2mol/L, and citric acid concentration is 0.2mol/L, respectively after the dissolving, SnCl
4Solution is poured in the citric acid solution.
(2), the weight of C is to take by weighing at 1: 2 by the mol ratio of Sn and C, and it is slowly poured in the 1 step solution for preparing, and it is carried out ultrasonic concussion 30 minutes.
Adopt the room temperature galvanic deposit 1 hour in above solution of Fig. 1 a device, the galvanic deposit current density is 100mA/cm
2, magnetic agitation.
Adopt centrifugal method separation of Sn-C powder, reaction soln and the good carbon dust of plating are put into together the test tube of whizzer.It is 2000r that centrifuge speed adopts rotating speed, and each centrifugation time is 3 minutes.Carry out centrifugal treating altogether ten times (preceding nine times use deionized water, use ethanol for the last time).The powder that obtains 100 ℃ of bakings 1 hour under vacuum condition are taken out stand-by.
(3), take by weighing the carbon of 10% powder weight and powder mixed grinding evenly in agate mortar of above acquisition by weight.
By weight for powder-carbon: styrene-butadiene rubber(SBR): thickening material: deionized water is 1000: 50: 14: 1400 ratio is powder-carbon of obtaining, styrene-butadiene rubber(SBR), and thickening material and deionized water are modulated pulping in beaker.Powder-carbon is mixed well slurry with slurry by mass ratio at 1: 1.464, spreads upon on the uneven surface of collector.Wait to do the back and go out circular electrode with punching pin, the gained sample is called the 2# sample.
Use tabletting machine with the 2# specimen electrode compression moulding of preparation as positive pole, be negative pole with the lithium sheet, with the capillary polypropylene barrier film, electrolytic solution is 1M LiPF between positive pole and the negative pole
6/ EC+DMC (1: 1), M represents volumetric molar concentration.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt blue electric battery test system at room temperature to carry out the constant current charge-discharge test, the specific storage curve is seen 2# sample shown in Figure 2.
Embodiment 3
1. solvent is distilled water or deionized water, and solute is a tin chloride, and concentration is at 0.1mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt, and concentration is at 0.3mol/L;
3. solvent is distilled water or deionized water, and solute is disodium EDTA (EDTA), and solute concentration is respectively at 0.1mol/L;
4. solvent is distilled water or deionized water, and solute is a citric acid, and solute concentration is respectively at 0.3 mol/L;
5. a certain amount of carbon particles is placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 60 minutes;
6. the solution that 1 step is prepared is slowly poured in the solution that 3 steps prepare;
7. the solution that 2 steps are prepared is slowly poured in the solution that 4 steps prepare;
8. the solution that 6,7 steps are prepared mixes;
9. the solution that 5 steps are prepared is slowly poured in the solution that 8 steps prepare, and it is carried out ultrasonic concussion 60 minutes can be stand-by.
Adopt the room temperature galvanic deposit 1 hour in above solution of Fig. 1 C device, the galvanic deposit current density is 100mA/cm
2, magnetic agitation.Adopt centrifugal method separation of Sn-Co-C powder, gained solution is put into the test tube of whizzer.It is 2000r that centrifuge speed adopts rotating speed, and each centrifugation time is 3 minutes.Carry out centrifugal treating altogether ten times (preceding nine times use washed with de-ionized water, clean with ethanol for the last time).The Sn-Co-C powder that obtains 100 ℃ of bakings 1 hour under vacuum condition are taken out stand-by.
Be the Sn-Co-C powder by weight: styrene-butadiene rubber(SBR): thickening material: deionized water is 1000: 50: 14: 1400 ratio is modulated pulping in beaker, spreads upon on the uneven surface of collector.Wait to do the back and go out circular electrode with punching pin.
Use tabletting machine with the specimen electrode compression moulding of preparation as positive pole, be negative pole with the lithium sheet, with the capillary polypropylene barrier film, electrolytic solution is 1M LiPF between positive pole and the negative pole
6/ EC+DMC (1: 1), M represents volumetric molar concentration.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt blue electric battery test system at room temperature to carry out the constant current charge-discharge test, specific storage and efficiency curve are seen shown in Figure 3.
Claims (4)
1. a power by epitaxial cathode electrochemical codeposition technology prepares the method for metal, alloy, metal oxide and alloyed oxide composite powder, and it is characterized in that: its method steps is as follows:
The first step:
At first preparation prepares the electrolytic solution one of metal:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is disodium EDTA or citric acid and salt or pyrophosphate salt, and concentration is at 0.01～5mol/L;
3. the solution that 1 step is prepared is slowly poured in the solution that 2 steps prepare;
4. a certain amount of graphite or carbon black are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
5. the solution that 4 steps are prepared is slowly poured in the solution that 3 steps prepare, and it is carried out ultrasonic concussion 30-120 minute can be stand-by;
The electrolytic solution two of preparation preparation alloy:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt or sulfuric acid Cobalt or nitric acid Cobalt, and concentration is at 0.01～5mol/L;
3. solvent is distilled water or deionized water, and solute is disodium EDTA or citric acid and salt or pyrophosphate salt, and concentration is at 0.01～5mol/L;
4. a certain amount of graphite or carbon black are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
5. the solution that 1 step and 2 steps are prepared is slowly poured in the solution that 3 steps prepare;
6. the solution that 4 steps are prepared is slowly poured in the solution that 5 steps prepare, and it is carried out ultrasonic concussion 30-120 minute can be stand-by;
The electrolytic solution three of preparation preparation alloy:
1. solvent is distilled water or deionized water, and solute is tin chloride or tin sulphate, and concentration is at 0.01～5mol/L;
2. solvent is distilled water or deionized water, and solute is chlorination Cobalt or sulfuric acid Cobalt or nitric acid Cobalt, and concentration is at 0.01～5mol/L;
3. solvent is distilled water or deionized water, and solute is a Sunmorl N 60S, and solute concentration is respectively at 0.01～5mol/L;
4. solvent is distilled water or deionized water, and solute is a citric acid, and solute concentration is respectively at 0.01～5mol/L;
5. a certain amount of graphite or carbon black are placed palmityl trimethyl ammonium chloride solution, it is carried out ultrasonic concussion 30-120 minute;
6. the solution that 1 step is prepared is slowly poured in the solution that 3 steps prepare;
7. the solution that 2 steps are prepared is slowly poured in the solution that 4 steps prepare;
8. 6,7 steps ground solution was mixed in 1: 1 in molar ratio～1: 10 or 1: 10～1: 1;
9. the solution that 5 steps are prepared is slowly poured in the solution that 8 steps prepare in required ratio, and it is carried out ultrasonic concussion 30-120 minute can be stand-by;
Described " a certain amount of graphite " reaches weight that " in required ratio " be meant carbon is 1: 2 by the mol ratio of tin and carbon.
Second step: the electrolytic solution that the first step configures is put into plating tank, and anode and cathode is provided with and adopts mechanical type to stir pawl or magnetic stir bar respectively; Consider that the effect that utilizes gravity is easy to the carbon particles negative electrode that obtains to extend, so negative electrode is a sheet, is positioned over bottom land; Anode can adopt the disk shape, also can adopt strip, places the top respectively;
The 3rd step: galvanic deposit
Connect circuit and carry out galvanic deposit according to calculating the size of current energising; The galvanic deposit electric current is 1～10 ampere/square decimeter, and tank liquor temperature is 20～60 ℃, and electrodeposition time is 1～300 minute, and deposition process stirs with the little speed of agitator;
The 4th step: centrifugation powder
Adopt centrifugal method to separate powder, reaction soln and the good carbon dust of plating are put into together the test tube of whizzer; It is 500-6000 rev/min that centrifuge speed adopts rotating speed, and each centrifugation time is 1-30 minute; Carry out centrifugal treating altogether three～ten times, precedingly spend the ionized water rinsing several times, use the ethanol rinsing for the last time;
The 5th step: oven dry
The powder that the 4th step was obtained 100 ℃ of bakings 1 hour under vacuum condition are taken out stand-by;
The 6th step: thermal treatment
Needing acquisition metal oxide coating C powder or alloyed oxide to coat the C powder can heat-treat the powder in the 4th step under suitable oxidizing temperature;
2. prepare the method for metal, alloy, metal oxide and alloyed oxide composite powder according to the described power by epitaxial cathode electrochemical codeposition technology of claim 1, it is characterized in that: the negative electrode sheet described in this second step is a kind of metal electrode of making or porous foam nickel, porous foam copper or the porous foam aluminium in nickel foil, aluminium foil, Copper Foil, graphite, carbon fiber, nickel plate or the platinized platinum.
3. prepare the method for metal, alloy, metal oxide and alloyed oxide composite powder according to the described power by epitaxial cathode electrochemical codeposition technology of claim 1, it is characterized in that: this metal and alloy are tin and tin-cobalt.
4. prepare the method for metal, alloy, metal oxide and alloyed oxide composite powder according to the described power by epitaxial cathode electrochemical codeposition technology of claim 1, it is characterized in that: this metal oxide and alloyed oxide are tin-oxide and tin-cobalt/cobalt oxide.
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| CN2008100559212A CN101275256B (en) | 2008-01-02 | 2008-01-02 | Method for preparing metal, alloy, metallic oxide and alloy oxide composite power by epitaxial cathode electrochemical codeposition technology |
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| CN101877399B (en) * | 2010-06-30 | 2012-08-01 | 复旦大学 | Preparation method of three-dimensional porous tin-copper alloy cathode materials for lithium ion battery |
| JP5744313B2 (en) * | 2011-04-05 | 2015-07-08 | エルジー・ケム・リミテッド | Negative electrode active material for lithium secondary battery and method for producing the same |
| CN108265318B (en) * | 2016-12-30 | 2019-12-20 | 上海移宇科技股份有限公司 | Method and device for preparing flexible battery cathode powder |
| CN107326430A (en) * | 2017-06-23 | 2017-11-07 | 山东大学 | A kind of preparation method of new porous metals |
| CN107579207B (en) * | 2017-09-20 | 2019-11-22 | 吉林省凯禹电化学储能技术发展有限公司 | A kind of preparation method of negative plate of lead-carbon battery |
| CN108511703A (en) * | 2018-03-02 | 2018-09-07 | 合肥国轩高科动力能源有限公司 | Metal oxide coated layered positive electrode material and preparation method thereof |
| CN109755562A (en) * | 2018-12-29 | 2019-05-14 | 浙江南都电源动力股份有限公司 | The preparation method and applications of iron nickel oxide cladding carbon material |
| CN114774978B (en) * | 2022-05-10 | 2024-04-09 | 浙江工业大学 | Ni-Fe MMO film modified foam nickel catalyst and preparation method and application thereof |
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