CN103000906A - Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery - Google Patents
Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery Download PDFInfo
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- CN103000906A CN103000906A CN2012105362090A CN201210536209A CN103000906A CN 103000906 A CN103000906 A CN 103000906A CN 2012105362090 A CN2012105362090 A CN 2012105362090A CN 201210536209 A CN201210536209 A CN 201210536209A CN 103000906 A CN103000906 A CN 103000906A
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Abstract
The invention discloses a preparation method of a foamy copper/carbon nanophase composite negative electrode material for a lithium ion battery. The method comprises the steps that the foamy copper is obtained through the processes of mixing NaCl particles and electrolytic copper powder, briquetting the mixture into blanks, sintering the blanks, dissolving out the NaCl particles and reducing under the protection of hydrogen; the foamy copper loaded with a catalyst precursor is obtained by immersing the foamy copper in a catalyst solution prepared by nickel nitrate, yttrium nitrate or cobalt nitrate and calcining the foamy copper loaded with the catalyst; and the foamy copper/carbon nanophase composite electrode material is obtained via reduction of the foamy copper loaded with a catalyst precursor and growth in acetylene. The method is advantageous in that foamy copper with controllable porosity and aperture is employed as a current collector; and carbon nanophase with different morphologies which has good quality and high purity is grown on the foamy copper current collector directly by controlling doping and growing processes of the catalyst. The method is simple in preparation process, and is easy to realize and popularize. The composite negative electrode material has low preparation cost and good electrochemical performance.
Description
Technical field
The present invention relates to the preparation method of a kind of foam copper/carbon nanophase composite lithium ion battery cathode material, belong to the technology of preparing of lithium ion cell electrode.
Background technology
Lithium ion battery is as a kind of green energy resource, have that energy density is large, operating voltage is high, operating temperature range is large, have extended cycle life, memory-less effect, the advantage such as lightweight is widely used in portable electronics, electric motor car industry, military equipment and Space Industry etc.The negative material of lithium ion battery is one of key factor that affects battery performance, has determined capacity and the cycle performance of lithium ion battery.At present, business-like lithium ion battery negative material is mainly graphited material with carbon element, and the carbon nanomaterials such as carbon nano-tube (CNTs) and carbon nano-fiber (CNFs) are owing to have excellent physics and chemical characteristic and embedding lithium performance so that the insert depth of lithium ion is little, the short embedded location of stroke is many, in the pipe and the hole, slit of interlayer, it is fine that carbon nanomaterial flies electric conductivity simultaneously, and specific area is large, preferably ion transportation and electronic conduction ability are arranged, attract wide attention.
At present, existing Many researchers has been studied the embedding lithium characteristic of carbon nanophase as lithium ion battery electrode material.In addition, the carbon nanophase can also directly join in the electrode as conductive agent and use.As active intercalation materials of li ions, the conventional electrodes preparation process need to evenly be coated in (such as Copper Foil, aluminium foil, foam copper, foamed aluminium, foam iron, nickel foam etc.) on the collector with itself and binding agent, drying, compressing tablet, punching are made again, its preparation process is complicated, the adding of binding agent can form stable compound such as (PVDF) with electrode carbon material and lithium metal, can cause capacitance loss, electrode conductivuty reduces, battery security reduces, wayward and the uneven thickness of coating viscosity causes the dispersiveness reduction of carbon nanophase can limit giving full play to of its performance equally; Use as conductive agent, the dispersiveness of carbon nanophase is more important.Therefore, binding agent is not adopted in research, causes carbon nanophase good dispersion and preparation technology simple, easily produces, and the carbon negative pole material of good cycling stability is significant.Do not adopt at present chemical vapour deposition technique directly in the preparation method of foam copper growth carbon nanophase negative material, adopt this preparation method, the inner three-dimensional conductive network that connects continuously that forms of electrode material, can economize the adding of no-bonder, the Uniform Dispersion of carbon nanophase can be realized again, and the technological parameter of CVD synthesize nano carbon material can be optimized.
To sum up, the invention provides a kind of preparation method making the lithium ion battery negative of direct growth carbon nanophase on the foam copper by oneself, wherein the carbon nanophase comprises carbon nano-tube, single double helix carbon nano-fiber, noodles shape carbon fiber etc.The method preparation technology is simple, and cost is low, carbon nanophase quality and the purity advantages of higher of growth, and the chemical property of acquisition is good.
Summary of the invention
The object of the invention is to provide the preparation method of a kind of foam copper/carbon nanophase composite lithium ion battery cathode.The method preparation technology is simple, and cost is low, chemical property is good.
The present invention is achieved by the following technical solutions, the preparation method of a kind of foam copper/carbon nanophase composite lithium ion battery cathode, wherein the carbon nanophase comprises carbon nano-tube, single double helix carbon nano-fiber, noodles shape carbon nano-fiber, it is characterized in that comprising following process:
1. the preparation of foam copper
1) the NaCl particle with average grain diameter 0.5mm is 1:(1 ~ 20 in ratio of grinding media to material), rotating speed is 100 ~ 500rpm, and Ball-milling Time is to carry out ball milling under the condition of 10 ~ 90min, and obtaining particle diameter is the NaCl particle of 40 ~ 110 μ m;
2) NaCl particle and the 200 order electrolytic copper powders step 1) processed are 1:(0.24 ~ 1.37 according to mass ratio), drip absolute ethyl alcohol to moistening mixing, mixture is packed into to suppress is of a size of Φ 12 * (40 ~ 0.14) mm
3Mould in, compressing;
3) with step 2) tube furnace that places of the blank that makes, pass into argon gas take flow velocity as 150 ~ 300mL/min, be warming up to simultaneously 740 ~ 780 ℃ of sintering 1 ~ 3h take heating rate as 3 ~ 10 ℃/min, then be warming up to again 920 ~ 950 ℃ of sintering 1.5 ~ 3.5 h take heating rate as 3 ~ 10 ℃/min, obtaining the sintering blank through naturally cooling off;
4) with the sintering blank of step 3), placing temperature is that 50 ~ 100 ℃ circulating hot water device is molten except the NaCl particle, in 50 ~ 100 ℃ of oven dry of temperature, the tube furnace that places again passes into argon gas take flow velocity as 150 ~ 300mL/min, and is warming up to 250 ~ 400 ℃ take heating rate as 3 ~ 10 ℃/min, after passing into again hydrogen 150 ~ 300mL/min reduction 1 ~ 3h, be down to room temperature, obtaining porosity is 50 ~ 85%, and the aperture is the foam copper of 40 ~ 110 μ m;
2. Kaolinite Preparation of Catalyst presoma on the foam copper matrix
The mol ratio of 1) pressing nickel and yttrium is (1-2): 1, with nickel nitrate and yttrium nitrate, add in deionized water or the absolute ethyl alcohol, and be mixed with and contain the catalyst solution that nickel ion concentration is 0.01-0.0001mol/L nickel nitrate and yttrium nitrate; Or cobalt nitrate added in deionized water or the absolute ethyl alcohol, be mixed with the catalyst solution that concentration of cobalt ions is 0.01-0.0001mol/L;
2) in the foam copper that wherein a kind of catalyst solution immersion step 1 obtains with the step 1) preparation, time is 1-30min, warp is at 80 ~ 100 ℃ of lower vacuumize 1 ~ 4h, obtaining load has the foam copper of catalyst, the foam copper of this supported catalyst is put into quartz boat, again quartz boat is placed on the flat-temperature zone of tube furnace, under argon shield, be warming up to 200 ~ 400 ℃ with 3 ~ 10 ℃/min of heating rate, calcining at constant temperature 1 ~ 4h has obtained the foam copper matrix that load has catalyst precursor;
3. the preparation of foam copper/carbon nanophase composite negative pole material
The load that step 2 is made has the foam copper matrix of catalyst precursor to be put in the quartz boat; quartz boat is placed the crystal reaction tube flat-temperature zone; under argon shield; after being warming up to 400 ℃ ~ 500 ℃ with 3 ~ 10 ℃/min of heating rate; pass into the hydrogen that flow velocity is 150 ~ 300mL/min in crystal reaction tube, reduction reaction 0.5h ~ 2h is under the argon shield; be warming up to 550 ℃ ~ 850 ℃ with 3 ~ 10 ℃/min of heating rate, and press argon gas and acetylene gas volume than being (10 ~ 50)
:1 gaseous mixture that passes into argon gas and acetylene gas carries out catalytic cracking reaction 0.2h ~ 1h, then under argon atmosphere furnace temperature is down to room temperature, obtains foam copper/carbon nanophase composite lithium ion battery cathode material;
The present invention has the following advantages: adopting porosity and the controlled foam copper in aperture is collector, doping, catalyst concn and growth temperature etc. by the control catalyst, directly grown the carbon nanophase of the different-shape that quality is good and purity is high at the foam copper collector, the carbon nanophase comprises carbon nano-tube, single double helix carbon nano-fiber, noodles shape carbon fiber etc.The method preparation technology is simple, and cost is low, chemical property is good, is easy to realize and promote.The method also can adopt other catalyst solutions to be widely used in the preparation of foamed aluminium, nickel foam/carbon nanophase composite lithium ion cell electrode simultaneously.
Description of drawings
Fig. 1 is the SEM photo of the foam copper sample that makes of the embodiment of the invention one.
Fig. 2 is the SEM photo of the foam copper that makes of the embodiment of the invention one/carbon nano-tube composite lithium ion battery cathode material;
Fig. 3 is the TEM photo of the foam copper that makes of the embodiment of the invention one/carbon nano-tube composite lithium ion battery cathode material;
Fig. 4 is the SEM photo of the foam copper that makes of the embodiment of the invention two/single-screw carbon nano-fiber composite lithium ion battery cathode material;
Fig. 5 is the TEM photo of the foam copper that makes of the embodiment of the invention two/single-screw carbon nano-fiber composite lithium ion battery cathode material;
Fig. 6 is the SEM photo of the foam copper that makes of the embodiment of the invention three/double helix carbon fiber composite lithium ion battery cathode material;
Fig. 7 is the TEM photo of the foam copper that makes of the embodiment of the invention three/double helix carbon fiber composite lithium ion battery cathode material;
Fig. 8 is the SEM photo of the foam copper that makes of the embodiment of the invention four/noodles shape carbon fiber composite lithium ion battery cathode material;
Fig. 9 is the TEM photo of the foam copper that makes of the embodiment of the invention four/noodles shape carbon fiber composite lithium ion battery cathode material;
Figure 10 is the foam copper that makes of the embodiment of the invention one/1C of carbon nano-tube composite lithium ion battery cathode material and the charge-discharge performance under the 2C.
Figure 11 is the foam copper that makes of the embodiment of the invention two/1C of single-screw carbon fiber composite lithium ion battery cathode material and the charge-discharge performance under the 2C.
Figure 12 is the high rate performance of the foam copper that makes of the embodiment of the invention one/carbon nano-tube composite lithium ion battery cathode material.
Figure 13 is the high rate performance of the foam copper that makes of the embodiment of the invention two/single-screw carbon fiber composite lithium ion battery cathode material.
Embodiment
Further specify the present invention below in conjunction with embodiment, these embodiment only are used for explanation the present invention, do not limit the present invention.
Embodiment one
Be 20:1 with the 10gNaCl particle in ratio of grinding media to material, rotating speed is 500rpm, ball milling 60min, obtaining average grain diameter is the NaCl particle of 40 μ m, get the 2.41g particle diameter and be the NaCl particle of 40 μ m and 10g electrolytic copper powder and 5mL absolute ethyl alcohol and put into the V-type drum mixer, rotating speed is 80r/min, and incorporation time is 3h, and the compacting of packing into of the mixture of then getting 30mgNaCl and copper powder is of a size of Φ 12 * 0.14mm
3Mould in, the unidirectional 300MPa that is forced into obtains blank.The above-mentioned blank that makes is placed tube furnace, under the protective atmosphere of argon gas, be warming up to 760 ℃ with the heating rate of 10 ℃/min, temperature retention time is 2h, then is being warming up to 940 ℃ of insulation 3h, and the rate of temperature fall with 10 ℃/min cools to room temperature with the furnace equally.Take out this sample and place 80 ℃ of circulating hot water device stripping NaCl, then place baking oven 100 ℃ of oven dry, put into tube furnace after being cooled to room temperature, the speed with 10 ℃/min under the protection argon gas atmosphere is warming up to 350 ℃, passes into H take flow velocity as 200mL/min
2Close H behind the reduction 1.5h
2, pass into and take out after argon gas is down to room temperature with the stove cooling, namely making porosity is 50%, average pore size is the foam copper of 40 μ m, as shown in Figure 1;
Take by weighing respectively 0.0145g six water nickel nitrates and 0.0063g six water yttrium nitrates; dissolve in the 50mL deionized water; be mixed with the solution of 0.001mol/L; adopt vacuum impregnation technology that the catalyst solution of preparation is immersed in the foam copper sample; time is 30min; there is the foam copper of catalyst to take out load; then after placing 100 ℃ of lower vacuumize 1h of vacuum drying chamber; put it in the quartz boat; place the constant temperature zone, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield; rise to 400 ℃ of temperature with 10 ℃/min of heating rate; calcining at constant temperature 2 hours, then rise to 450 ℃ with 10 ℃/min of heating rate crystal reaction tube after, pass into hydrogen take flow velocity as 200mL/min to crystal reaction tube and carry out reduction reaction 2h; then close hydrogen; pass into argon gas, rise to 600 ℃ of temperature with 10 ℃/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas behind temperature stabilization carries out catalytic cracking reaction 0.5h; wherein, the volume ratio of argon gas and acetylene gas is 240
:6, then under argon atmosphere, furnace temperature is down to room temperature, obtain carbon nano-tube combination electrode material on the foam copper matrix.
Take the above-mentioned foam copper/carbon nano-tube that makes as work electrode, take metal lithium sheet as to electrode, barrier film is the Celgard2400 microporous polypropylene membrane, the LiPF of 1mol/L
6(EMC:EC:DEC=1:1:1) solution is electrolyte, is encapsulated as half-cell, and model is CR2032.Adopt ESEM and transmission electron microscope to characterize microscopic appearance and the structure (as shown in Figures 2 and 3) of synthesizing carbon nanotubes, adopt the cell tester of LAND Electronics Co., Ltd. to carry out electrochemical property test.It is carried out charge-discharge performance, cycle performance and high rate performance etc. analyze research, the result shows that its first discharge specific capacity is respectively 1238.3mAh/g, charge-discharge performance as shown in figure 10 under the multiplying power of 1C and 2C, circulate after 100 times, its specific discharge capacity is respectively 328.9mAh/g, obtained good electro-chemical properties, high rate performance as shown in figure 11.
Embodiment two
Be 20:1 with the 10gNaCl particle in ratio of grinding media to material, rotating speed is 300rpm, ball milling 90min, obtaining average grain diameter is the NaCl particle of 70 μ m, NaCl particle and the 10g particle diameter of getting the 3.62g particle diameter and be 70 μ m are that 200 order electrolytic copper powders and 6mL absolute ethyl alcohol are put into the V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 38mgNaCl and copper powder is packed into and is of a size of Φ 12 * 0.20mm
3Compacting tool set in, unidirectionally be forced into the blank that 300MPa obtains.The above-mentioned blank that makes is placed tube furnace, under the protective atmosphere of argon gas, be warming up to 750 ℃ with the heating rate of 10 ℃/min, temperature retention time is 2h, then is being warming up to 950 ℃ of insulation 3h, and the rate of temperature fall with 10 ℃/min cools to room temperature with the furnace equally.Take out this sample and place 80 ℃ of circulating hot water devices to remove the NaCl particle is molten, then place baking oven 100 ℃ of oven dry, put into tube furnace after being cooled to room temperature, the speed with 10 ℃/min under the protection argon gas atmosphere is warming up to 400 ℃, passes into H
2Close H behind the reduction 1h
2, pass into and take out after argon gas is down to room temperature with the stove cooling, namely making porosity is 60%, average pore size is the through-hole foam copper of 70 μ m.
Take by weighing respectively 0.145g six water nickel nitrates and 0.063g six water yttrium nitrates; dissolve in the 50mL deionized water; be mixed with the solution of 0.01mol/L; adopt vacuum impregnation technology that the catalyst solution of preparation is immersed in the foam copper sample; time is 30min; there is the foam copper of catalyst to take out load; then after placing 100 ℃ of lower vacuumize 1h of vacuum drying chamber; put it in the quartz boat; place the constant temperature zone, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield; rise to 400 ℃ of temperature with 5 ℃/min of heating rate; calcining at constant temperature 1 hour, then rise to 450 ℃ with 10 ℃/min of heating rate crystal reaction tube after, pass into hydrogen take flow velocity as 150mL/min to crystal reaction tube and carry out reduction reaction 1h; then close hydrogen; pass into argon gas, rise to 600 ℃ of temperature with 10 ℃/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas behind temperature stabilization carries out catalytic cracking reaction 0.5h; wherein, the volume ratio of argon gas and acetylene gas is 240
:6, then under argon atmosphere, furnace temperature is down to room temperature, obtain growth single-screw carbon fiber combination electrode material on the foam copper matrix.
Take the above-mentioned foam copper that makes/single-screw carbon fiber as work electrode, take metal lithium sheet as to electrode, barrier film is the Celgard2400 microporous polypropylene membrane, the LiPF of 1mol/L
6(EMC:EC:DEC=1:1:1) solution is electrolyte, is encapsulated as half-cell, and model is CR2032.Adopt ESEM and transmission electron microscope to characterize microscopic appearance and the structure (as shown in Figure 4 and Figure 5) of synthesizing carbon nanotubes, adopt the cell tester of LAND Electronics Co., Ltd. to carry out electrochemical property test.It is carried out charge-discharge performance, cycle performance and high rate performance etc. analyze research, the result shows that its first discharge specific capacity is respectively 1402.6mAh/g, charge-discharge performance as shown in figure 12 under the multiplying power of 1C and 2C, circulate after 100 times, its specific discharge capacity is respectively 340.1mAh/g, obtained good electro-chemical properties, high rate performance as shown in figure 13.
Embodiment three
Be 20:1 with the 10gNaCl particle in ratio of grinding media to material, rotating speed is 400rpm, ball milling 90min, obtaining average grain diameter is the NaCl particle of 60 μ m, NaCl particle and the 10g particle diameter of getting the 5.60g particle diameter and be 60 μ m are that 200 order electrolytic copper powders and 6mL absolute ethyl alcohol are put into the V-type drum mixer, rotating speed is 80r/min, and incorporation time is 4h, and the mixture of then getting 46mgNaCl and copper powder is packed into and is of a size of Φ 12 * 0.34mm
3Compacting tool set in, the unidirectional 300MPa that is forced into obtains blank.The above-mentioned blank that makes is placed tube furnace, under the protective atmosphere of argon gas, be warming up to 740 ℃ with the heating rate of 8 ℃/min, temperature retention time is 3h, then is being warming up to 940 ℃ of insulation 1.5h, and the rate of temperature fall with 10 ℃/min cools to room temperature with the furnace equally.Take out this sample and place 50 ℃ of circulating hot water devices to remove the NaCl particle is molten, then place baking oven 100 ℃ of oven dry, put into tube furnace after being cooled to room temperature, the speed with 10 ℃/min under the protection argon gas atmosphere is warming up to 250 ℃, passes into H
2Close H behind the reduction 1h
2, pass into and take out after argon gas is down to room temperature with the stove cooling, namely making porosity is 70%, average pore size is the through-hole foam copper of 60 μ m.
Take by weighing respectively 0.145g six water nickel nitrates and 0.063g six water yttrium nitrates; dissolve in the 50mL absolute ethyl alcohol; be mixed with the solution of 0.01mol/L; adopt vacuum impregnation technology that the catalyst solution of preparation is immersed in the foam copper sample; time is 1min; there is the foam copper of catalyst to take out load; then after placing 90 ℃ of lower vacuumize 2h of vacuum drying chamber; put it in the quartz boat; place the constant temperature zone, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield; rise to 200 ℃ of temperature with 10 ℃/min of heating rate; calcining at constant temperature 4 hours, then rise to 500 ℃ with 10 ℃/min of heating rate crystal reaction tube after, pass into hydrogen take flow velocity as 300mL/min to crystal reaction tube and carry out reduction reaction 0.5h; then close hydrogen; pass into argon gas, rise to 700 ℃ of temperature with 5 ℃/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas behind temperature stabilization carries out catalytic cracking reaction 0.2h; wherein, the volume ratio of argon gas and acetylene gas is 240
:6, then under argon atmosphere, furnace temperature is down to room temperature, obtain growth double helix carbon fiber combination electrode material on the foam copper matrix.
Take the above-mentioned foam copper that makes/double helix carbon fiber as work electrode, take metal lithium sheet as to electrode, barrier film is the Celgard2400 microporous polypropylene membrane, the LiPF of 1mol/L
6(EMC:EC:DEC=1:1:1) solution is electrolyte, is encapsulated as half-cell, and model is CR2032.Adopt ESEM and transmission electron microscope to characterize microscopic appearance and the structure (as shown in Figure 6 and Figure 7) of synthesizing carbon nanotubes, adopt the cell tester of LAND Electronics Co., Ltd. to carry out electrochemical property test.It is carried out charge-discharge performance, cycle performance and high rate performance etc. analyze research, the result shows that its first discharge specific capacity is respectively 767.5mAh/g, after charge and discharge cycles under the multiplying power of 1C 100 times, its specific discharge capacity is respectively 289.9mAh/g, has obtained good electro-chemical properties.
Embodiment four
Be 10:1 with the 10gNaCl particle in ratio of grinding media to material, rotating speed is 500rpm, ball milling 30min, obtaining average grain diameter is the NaCl particle of 90 μ m, NaCl particle and the 10g particle diameter of getting the 9.64g particle diameter and be 90 μ m are that 200 order electrolytic copper powders and 8mL absolute ethyl alcohol are put into the V-type drum mixer, rotating speed is 80r/min, and incorporation time is 1h, and the mixture of then getting 52mgNaCl and copper powder is packed into and is of a size of Φ 12 * 0.46mm
3Compacting tool set in, the unidirectional 300MPa that is forced into obtains blank.The above-mentioned blank that makes is placed tube furnace, under the protective atmosphere of argon gas, be warming up to 780 ℃ with the heating rate of 8 ℃/min, temperature retention time is 1h, then is being warming up to 950 ℃ of insulation 3.5h, and the rate of temperature fall with 8 ℃/min cools to room temperature with the furnace equally.Take out this sample and place 100 ℃ of circulating hot water devices to remove the NaCl particle is molten, then place baking oven 100 ℃ of oven dry, put into tube furnace after being cooled to room temperature, the speed with 8 ℃/min under the protection argon gas atmosphere is warming up to 250 ℃, passes into H
2Close H behind the reductase 12 h
2, pass into and take out after argon gas is down to room temperature with the stove cooling, namely making porosity is 80%, average pore size is the through-hole foam copper of 90 μ m.
Take by weighing respectively 0.0029g six water nickel nitrates and 0.0013g six water yttrium nitrates; dissolve in the 100mL absolute ethyl alcohol; be mixed with the solution of 0.0001mol/L; adopt vacuum impregnation technology that the catalyst solution of preparation is immersed in the foam copper sample; time is 1min; there is the foam copper of catalyst to take out load; then after placing 80 ℃ of lower vacuumize 4h of vacuum drying chamber; put it in the quartz boat; place the constant temperature zone, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield; rise to 300 ℃ of temperature with 10 ℃/min of heating rate; calcining at constant temperature 2 hours, then rise to 400 ℃ with 3 ℃/min of heating rate crystal reaction tube after, pass into hydrogen take flow velocity as 150mL/min to crystal reaction tube and carry out reduction reaction 2h; then close hydrogen; pass into argon gas, rise to 800 ℃ of temperature with 10 ℃/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas behind temperature stabilization carries out catalytic cracking reaction 1h; wherein, the volume ratio of argon gas and acetylene gas is 300
:6, then under argon atmosphere, furnace temperature is down to room temperature, obtain aufwuchsplate strip carbon fiber combination electrode material on the foam copper matrix.
Take the above-mentioned foam copper that makes/noodles shape carbon fiber as work electrode, take metal lithium sheet as to electrode, barrier film is the Celgard2400 microporous polypropylene membrane, the LiPF of 1mol/L
6(EMC:EC:DEC=1:1:1) solution is electrolyte, is encapsulated as half-cell, and model is CR2032.Adopt ESEM and transmission electron microscope to characterize microscopic appearance and the structure (such as Fig. 8 and shown in Figure 9) of synthesizing carbon nanotubes, adopt the cell tester of LAND Electronics Co., Ltd. to carry out electrochemical property test.It is carried out charge-discharge performance, cycle performance and high rate performance etc. analyze research, the result shows that its first discharge specific capacity is respectively 656.9mAh/g, after charge and discharge cycles under the multiplying power of 1C 100 times, its specific discharge capacity is respectively 205.7mAh/g, has obtained good electro-chemical properties.
Embodiment five
Be 1:1 with the 10gNaCl particle in ratio of grinding media to material, rotating speed is 100rpm, ball milling 90min, obtaining average grain diameter is the NaCl particle of 110 μ m, NaCl particle and the 10g particle diameter of getting the 5.60g particle diameter and be 110 μ m are that 200 order electrolytic copper powders and 6mL absolute ethyl alcohol are put into the V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 52mgNaCl and copper powder is packed into and is of a size of Φ 12 * 0.54mm
3Compacting tool set in, the unidirectional 300MPa that is forced into obtains blank.The above-mentioned blank that makes is placed tube furnace, under the protective atmosphere of argon gas, be warming up to 740 ℃ with the heating rate of 8 ℃/min, temperature retention time is 3h, then is being warming up to 920 ℃ of insulation 3.5h, and the rate of temperature fall with 10 ℃/min cools to room temperature with the furnace equally.Take out this sample and place 60 ℃ of circulating hot water devices to remove the NaCl particle is molten, then place baking oven 100 ℃ of oven dry, put into tube furnace after being cooled to room temperature, the speed with 8 ℃/min under the protection argon gas atmosphere is warming up to 250 ℃, passes into H
2Close H behind the reduction 1h
2, pass into and take out after argon gas is down to room temperature with the stove cooling, namely making porosity is 70%, average pore size is the through-hole foam copper of 110 μ m.
Take by weighing respectively 0.029g six water nickel nitrates and 0.013g six water yttrium nitrates; dissolve in the 100mL deionized water; be mixed with the solution of 0.001mol/L; adopt vacuum impregnation technology that the catalyst solution of preparation is immersed in the foam copper sample; time is 10min; there is the foam copper of catalyst to take out load; then after placing 90 ℃ of lower vacuumize 2h of vacuum drying chamber; put it in the quartz boat; place the constant temperature zone, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield; rise to 300 ℃ of temperature with 10 ℃/min of heating rate; calcining at constant temperature 3 hours, then rise to 500 ℃ with 9 ℃/min of heating rate crystal reaction tube after, pass into hydrogen take flow velocity as 300mL/min to crystal reaction tube and carry out reduction reaction 0.5h; then close hydrogen; pass into argon gas, rise to 800 ℃ of temperature with 10 ℃/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas behind temperature stabilization carries out catalytic cracking reaction 1h; wherein, the volume ratio of argon gas and acetylene gas is 500
:10, then under argon atmosphere, furnace temperature is down to room temperature, obtain growth straight tube-like carbon fiber combination electrode material on the foam copper matrix.
Embodiment six
Be 10:1 with the 10gNaCl particle in ratio of grinding media to material, rotating speed is 300rpm, ball milling 90min, obtaining average grain diameter is the NaCl particle of 80 μ m, NaCl particle and the 10g particle diameter of getting the 5.60g particle diameter and be 80 μ m are that 200 order electrolytic copper powders and 7mL absolute ethyl alcohol are put into the V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 60mgNaCl and copper powder is packed into and is of a size of Φ 12 * 0.60mm
3Compacting tool set in, the unidirectional 300MPa that is forced into obtains blank.The above-mentioned blank that makes is placed tube furnace, under the protective atmosphere of argon gas, be warming up to 760 ℃ with the heating rate of 8 ℃/min, temperature retention time is 2h, then is being warming up to 930 ℃ of insulation 2.5h, and the rate of temperature fall with 8 ℃/min cools to room temperature with the furnace equally.Take out this sample and place 80 ℃ of circulating hot water devices to remove the NaCl particle is molten, then place baking oven 100 ℃ of oven dry, put into tube furnace after being cooled to room temperature, the speed with 8 ℃/min under the protection argon gas atmosphere is warming up to 200 ℃, passes into H
2Close H behind the reduction 1.5h
2, pass into and take out after argon gas is down to room temperature with the stove cooling, namely making porosity is 70%, average pore size is the through-hole foam copper of 80 μ m.
Take by weighing respectively the 0.29g cobalt nitrate hexahydrate; dissolve in the 100mL absolute ethyl alcohol; be mixed with the solution of 0.01mol/L; adopt vacuum impregnation technology that the catalyst solution of preparation is immersed in the foam copper sample; time is 20min; there is the foam copper of catalyst to take out load; then after placing 100 ℃ of lower vacuumize 4h of vacuum drying chamber; put it in the quartz boat; place the constant temperature zone, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield; rise to 400 ℃ of temperature with 8 ℃/min of heating rate; calcining at constant temperature 4 hours, then rise to 500 ℃ with 10 ℃/min of heating rate crystal reaction tube after, pass into hydrogen take flow velocity as 150mL/min to crystal reaction tube and carry out reduction reaction 2h; then close hydrogen; pass into argon gas, rise to 600 ℃ of temperature with 10 ℃/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas behind temperature stabilization carries out catalytic cracking reaction 1h; wherein, the volume ratio of argon gas and acetylene gas is 600
:10, then under argon atmosphere, furnace temperature is down to room temperature, obtain growth different-shape carbon fiber mixed structure combination electrode material on the foam copper matrix.
Embodiment seven
Be 20:1 with the 10gNaCl particle in ratio of grinding media to material, rotating speed is 400rpm, ball milling 90min, obtaining average grain diameter is the NaCl particle of 60 μ m, NaCl particle and the 10g particle diameter of getting the 9.64g particle diameter and be 60 μ m are that 200 order electrolytic copper powders and 8mL absolute ethyl alcohol are put into the V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 60mgNaCl and copper powder is packed into and is of a size of Φ 12 * 0.60mm
3Compacting tool set in, the unidirectional 300MPa that is forced into obtains blank.The above-mentioned blank that makes is placed tube furnace, under the protective atmosphere of argon gas, be warming up to 780 ℃ with the heating rate of 10 ℃/min, temperature retention time is 1h, then is being warming up to 950 ℃ of insulation 1.5h, and the rate of temperature fall with 8 ℃/min cools to room temperature with the furnace equally.Take out this sample and place 100 ℃ of circulating hot water devices to remove the NaCl particle is molten, then place baking oven 100 ℃ of oven dry, put into tube furnace after being cooled to room temperature, the speed with 10 ℃/min under the protection argon gas atmosphere is warming up to 400 ℃, passes into H
2Close H behind the reduction 1h
2, pass into and take out after argon gas is down to room temperature with the stove cooling, namely making porosity is 80%, average pore size is the through-hole foam copper of 60 μ m.
Take by weighing respectively the 0.29g cobalt nitrate hexahydrate; dissolve in the 50mL absolute ethyl alcohol; be mixed with the solution of 0.005mol/L; adopt vacuum impregnation technology that the catalyst solution of preparation is immersed in the foam copper sample; time is 30min; there is the foam copper of catalyst to take out load; then after placing 100 ℃ of lower vacuumize 1h of vacuum drying chamber; put it in the quartz boat; place the constant temperature zone, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield; rise to 400 ℃ of temperature with 10 ℃/min of heating rate; calcining at constant temperature 1.5 hours, then rise to 500 ℃ with 5 ℃/min of heating rate crystal reaction tube after, pass into hydrogen take flow velocity as 150mL/min to crystal reaction tube and carry out reduction reaction 1.5h; then close hydrogen; pass into argon gas, rise to 700 ℃ of temperature with 10 ℃/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas behind temperature stabilization carries out catalytic cracking reaction 1h; wherein, the volume ratio of argon gas and acetylene gas is 500
:10, then under argon atmosphere, furnace temperature is down to room temperature, obtain growth different-shape carbon fiber mixed structure combination electrode material on the foam copper matrix.
Claims (1)
1. the preparation method of foam copper/carbon nanophase composite lithium ion battery cathode, wherein the carbon nanophase comprises carbon nano-tube, single double helix carbon nano-fiber and noodles shape carbon nano-fiber, it is characterized in that comprising following process:
1) preparation of foam copper
(1) the NaCl particle with average grain diameter 0.5mm is 1:(1 ~ 20 in ratio of grinding media to material), rotating speed is 100 ~ 500rpm, and Ball-milling Time is to carry out ball milling under the condition of 10 ~ 90min, and obtaining particle diameter is the NaCl particle of 40 ~ 110 μ m;
(2) NaCl particle and the 200 order electrolytic copper powders step (1) processed are 1:(0.24 ~ 1.37 according to mass ratio), drip absolute ethyl alcohol to moistening mixing, mixture is packed into to suppress is of a size of Φ 12 * (40 ~ 0.14) mm
3Mould in, compressing;
(3) tube furnace that the blank that step (2) is made places, pass into argon gas take flow velocity as 150 ~ 300mL/min, be warming up to simultaneously 740 ~ 780 ℃ of sintering 1 ~ 3h take heating rate as 3 ~ 10 ℃/min, then be warming up to again 920 ~ 950 ℃ of sintering 1.5 ~ 3.5 h take heating rate as 3 ~ 10 ℃/min, obtaining the sintering blank through naturally cooling off;
(4) with the sintering blank of step (3), placing temperature is that 50 ~ 100 ℃ circulating hot water device is molten except the NaCl particle, in 50 ~ 100 ℃ of oven dry of temperature, the tube furnace that places again passes into argon gas take flow velocity as 150 ~ 300mL/min, and is warming up to 250 ~ 400 ℃ take heating rate as 3 ~ 10 ℃/min, after passing into again hydrogen 150 ~ 300mL/min reduction 1 ~ 3h, be down to room temperature, obtaining porosity is 50 ~ 85%, and the aperture is the foam copper of 40 ~ 110 μ m;
2) Kaolinite Preparation of Catalyst presoma on the foam copper matrix
The mol ratio of (1) pressing nickel and yttrium is (1-2): 1, with nickel nitrate and yttrium nitrate, add in deionized water or the absolute ethyl alcohol, and be mixed with and contain the catalyst solution that nickel ion concentration is 0.01-0.0001mol/L nickel nitrate and yttrium nitrate; Or cobalt nitrate added in deionized water or the absolute ethyl alcohol, be mixed with the catalyst solution that concentration of cobalt ions is 0.01-0.0001mol/L;
(2) in the foam copper that wherein a kind of catalyst solution immersion step 1) obtains with step (1) preparation, time is 1-30min, warp is at 80 ~ 100 ℃ of lower vacuumize 1 ~ 4h, obtaining load has the foam copper of catalyst, the foam copper of this supported catalyst is put into quartz boat, again quartz boat is placed on the flat-temperature zone of tube furnace, under argon shield, be warming up to 200 ~ 400 ℃ with 3 ~ 10 ℃/min of heating rate, calcining at constant temperature 1 ~ 4h has obtained the foam copper matrix that load has catalyst precursor;
3) preparation of foam copper/carbon nanophase composite negative pole material
With step 2) load that makes has the foam copper matrix of catalyst precursor to be put in the quartz boat; quartz boat is placed the crystal reaction tube flat-temperature zone; under argon shield; after being warming up to 400 ℃ ~ 500 ℃ with 3 ~ 10 ℃/min of heating rate; in crystal reaction tube, pass into the hydrogen that flow velocity is 150 ~ 300mL/min; reduction reaction 0.5h ~ 2h; under the argon shield; be warming up to 550 ℃ ~ 850 ℃ with 3 ~ 10 ℃/min of heating rate; and by argon gas and acetylene gas volume than being (10 ~ 50): 1 gaseous mixture that passes into argon gas and acetylene gas carries out catalytic cracking reaction 0.2h ~ 1h; then under argon atmosphere, furnace temperature is down to room temperature, obtains foam copper/carbon nanophase composite lithium ion battery cathode material.
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