CN103000906B - 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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- CN103000906B CN103000906B CN201210536209.0A CN201210536209A CN103000906B CN 103000906 B CN103000906 B CN 103000906B CN 201210536209 A CN201210536209 A CN 201210536209A CN 103000906 B CN103000906 B CN 103000906B
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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 a kind of preparation method 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 affecting 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) make the insert depth of lithium ion little owing to having excellent physics and chemical characteristic and embedding lithium performance, the short embedded location of stroke is many, in pipe and the hole, gap of interlayer, it is fine that carbon nanomaterial flies electric conductivity simultaneously, and specific area is large, there are good ion transportation and electronic conduction ability, 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, carbon nanophase can also directly join in electrode and use as conductive agent.As active intercalation materials of li ions, conventional electrodes preparation process need to evenly be coated on collector itself and binding agent (as Copper Foil, aluminium foil, foam copper, foamed aluminium, foam iron, nickel foam etc.), drying again, compressing tablet, punching is made, its preparation process complexity, adding as (PVDF) of binding agent can form stable compound 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, cause the dispersiveness reduction of carbon nanophase can limit equally giving full play to of its performance, use as conductive agent, the dispersiveness of carbon nanophase is more important.Therefore, research does not adopt binding agent, 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 directly the grow preparation method of carbon nanophase negative material of chemical vapour deposition technique on foam copper, adopt this preparation method, the inner three-dimensional conductive network connecting continuously that forms of electrode material, can economize adding of no-bonder, the dispersed 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 foam copper by oneself, wherein 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 a kind of preparation method 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, a kind of preparation method of foam copper/carbon nanophase composite lithium ion battery cathode, wherein 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) be 1:(1 ~ 20 by the NaCl particle of average grain diameter 0.5mm in ratio of grinding media to material), rotating speed is 100 ~ 500rpm, carries out ball milling under the condition that Ball-milling Time is 10 ~ 90min, obtaining particle diameter is the NaCl particle of 40 ~ 110 μ m;
2) be 1:(0.24 ~ 1.37 by the NaCl particle of step 1) processing and 200 order electrolytic copper powders according to mass ratio), drip absolute ethyl alcohol to moistening mixing, pack mixture into compacting and be of a size of Φ 12 × (40 ~ 0.14) mm
3mould in, compressing;
3) by step 2) tube furnace that is placed in of the blank that makes, pass into argon gas taking flow velocity as 150 ~ 300mL/min, be warming up to 740 ~ 780 DEG C of sintering 1 ~ 3h simultaneously taking heating rate as 3 ~ 10 DEG C/min, then be warming up to again 920 ~ 950 DEG C of sintering 1.5 ~ 3.5 h taking heating rate as 3 ~ 10 DEG C/min, through the naturally cooling sintering blank that obtains;
4) by the sintering blank of step 3), the circulating hot water device that is placed in temperature and is 50 ~ 100 DEG C is molten except NaCl particle, in 50 ~ 100 DEG C of oven dry of temperature, the tube furnace being placed in again, passes into argon gas taking flow velocity as 150 ~ 300mL/min, and is warming up to 250 ~ 400 DEG C taking heating rate as 3 ~ 10 DEG C/min, pass into again after hydrogen 150 ~ 300mL/min reduction 1 ~ 3h, be down to room temperature, obtaining porosity is 50 ~ 85%, and aperture is the foam copper of 40 ~ 110 μ m;
2. Kaolinite Preparation of Catalyst presoma on foam copper matrix
1) mol ratio of pressing nickel and yttrium is (1-2): 1, by nickel nitrate and yttrium nitrate, add in deionized water or 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 is added in deionized water or 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 of being prepared by step 1), time is 1-30min, through vacuumize 1 ~ 4h at 80 ~ 100 DEG C, obtaining load has the foam copper of catalyst, the foam copper of this supported catalyst is put into quartz boat, then quartz boat is placed on to the flat-temperature zone of tube furnace, under argon shield, be warming up to 200 ~ 400 DEG C with 3 ~ 10 DEG C/min of heating rate, calcining at constant temperature 1 ~ 4h, having obtained load has the foam copper matrix of 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 quartz boat; quartz boat is placed in to crystal reaction tube flat-temperature zone; under argon shield; be warming up to after 400 DEG C ~ 500 DEG C with 3 ~ 10 DEG C/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 argon shield; be warming up to 550 DEG C ~ 850 DEG C with 3 ~ 10 DEG C/min of heating rate, and press argon gas and compare for (10 ~ 50) with acetylene gas volume
: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, by controlling doping, catalyst concn and the growth temperature etc. of catalyst, the carbon nanophase that has directly grown the different-shape that quality is good and purity is high on foam copper collector, 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.
Brief description of the drawings
Fig. 1 is the SEM photo of the foam copper sample that makes of the embodiment of the present invention one.
Fig. 2 is the SEM photo of foam copper/carbon nano-tube composite lithium ion battery cathode material of making of the embodiment of the present invention one;
Fig. 3 is the TEM photo of foam copper/carbon nano-tube composite lithium ion battery cathode material of making of the embodiment of the present invention one;
Fig. 4 is the SEM photo of foam copper/single-screw carbon nano-fiber composite lithium ion battery cathode material of making of the embodiment of the present invention two;
Fig. 5 is the TEM photo of foam copper/single-screw carbon nano-fiber composite lithium ion battery cathode material of making of the embodiment of the present invention two;
Fig. 6 is the SEM photo of foam copper/double helix carbon fiber composite lithium ion battery cathode material of making of the embodiment of the present invention three;
Fig. 7 is the TEM photo of foam copper/double helix carbon fiber composite lithium ion battery cathode material of making of the embodiment of the present invention three;
Fig. 8 is the SEM photo of foam copper/noodles shape carbon fiber composite lithium ion battery cathode material of making of the embodiment of the present invention four;
Fig. 9 is the TEM photo of foam copper/noodles shape carbon fiber composite lithium ion battery cathode material of making of the embodiment of the present invention four;
Figure 10 is the charge-discharge performance under 1C and the 2C of foam copper/carbon nano-tube composite lithium ion battery cathode material of making of the embodiment of the present invention one.
Figure 11 is the charge-discharge performance under 1C and the 2C of foam copper/single-screw carbon fiber composite lithium ion battery cathode material of making of the embodiment of the present invention two.
Figure 12 is the high rate performance of foam copper/carbon nano-tube composite lithium ion battery cathode material of making of the embodiment of the present invention one.
Figure 13 is the high rate performance of foam copper/single-screw carbon fiber composite lithium ion battery cathode material of making of the embodiment of the present invention two.
Embodiment
Further illustrate the present invention below in conjunction with embodiment, these embodiment, only for the present invention is described, do not limit the present invention.
Embodiment mono-
Be 20:1 by 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 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 V-type drum mixer, rotating speed is 80r/min, and incorporation time is 3h, and the mixture of then getting 30mgNaCl and copper powder packs compacting into and is of a size of Φ 12 × 0.14mm
3mould in, unidirectional be forced into 300MPa obtain blank.The above-mentioned blank making is placed in to tube furnace, under the protective atmosphere of argon gas, is warming up to 760 DEG C with the heating rate of 10 DEG C/min, temperature retention time is 2h, then, being warming up to 940 DEG C of insulation 3h, cools to room temperature with the furnace equally with the rate of temperature fall of 10 DEG C/min.Take out this sample and be placed in 80 DEG C of circulating hot water device stripping NaCl, be then placed in baking oven 100 DEG C of oven dry, put into tube furnace after being cooled to room temperature, under protection argon gas atmosphere, be warming up to 350 DEG C with the speed of 10 DEG C/min, pass into H taking flow velocity as 200mL/min
2after reduction 1.5h, close H
2, pass into after argon gas is down to room temperature with stove is cooling and take out, making porosity is 50%, average pore size is the foam copper of 40 μ m, as shown in Figure 1;
Take respectively 0.0145g six water nickel nitrates and 0.0063g six water yttrium nitrates, dissolve in 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 foam copper sample, time is 30min, there is the foam copper of catalyst to take out load, then be placed at 100 DEG C of vacuum drying chambers after vacuumize 1h, put it in quartz boat, be placed in the constant temperature region, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield, rise to 400 DEG C of temperature with 10 DEG C/min of heating rate, calcining at constant temperature 2 hours, then rise to after 450 DEG C with 10 DEG C/min of heating rate crystal reaction tube, pass into hydrogen taking 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 DEG C of temperature with 10 DEG C/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas after 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 foam copper matrix.
Taking the above-mentioned foam copper/carbon nano-tube making as work electrode, taking metal lithium sheet as to electrode, barrier film is 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 to the analysis and research such as charge-discharge performance, cycle performance and high rate performance, result shows that its first discharge specific capacity is respectively 1238.3mAh/g, under the multiplying power of 1C and 2C, charge-discharge performance as shown in figure 10, 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 bis-
Be 20:1 by 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 3.62g particle diameter and be 70 μ m are that 200 order electrolytic copper powders and 6mL absolute ethyl alcohol are put into V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 38mgNaCl and copper powder packs into and is of a size of Φ 12 × 0.20mm
3compacting tool set in, unidirectional be forced into 300MPa obtain blank.The above-mentioned blank making is placed in to tube furnace, under the protective atmosphere of argon gas, is warming up to 750 DEG C with the heating rate of 10 DEG C/min, temperature retention time is 2h, then, being warming up to 950 DEG C of insulation 3h, cools to room temperature with the furnace equally with the rate of temperature fall of 10 DEG C/min.Take out this sample and be placed in 80 DEG C of circulating hot water devices and remove molten NaCl particle, be then placed in baking oven 100 DEG C of oven dry, put into tube furnace after being cooled to room temperature, under protection argon gas atmosphere, be warming up to 400 DEG C with the speed of 10 DEG C/min, pass into H
2after reduction 1h, close H
2, pass into after argon gas is down to room temperature with stove is cooling and take out, making porosity is 60%, average pore size is the through-hole foam copper of 70 μ m.
Take respectively 0.145g six water nickel nitrates and 0.063g six water yttrium nitrates, dissolve in 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 foam copper sample, time is 30min, there is the foam copper of catalyst to take out load, then be placed at 100 DEG C of vacuum drying chambers after vacuumize 1h, put it in quartz boat, be placed in the constant temperature region, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield, rise to 400 DEG C of temperature with 5 DEG C/min of heating rate, calcining at constant temperature 1 hour, then rise to after 450 DEG C with 10 DEG C/min of heating rate crystal reaction tube, pass into hydrogen taking 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 DEG C of temperature with 10 DEG C/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas after 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, single-screw carbon fiber combination electrode material obtains growing on foam copper matrix.
Taking the above-mentioned foam copper/single-screw carbon fiber making as work electrode, taking metal lithium sheet as to electrode, barrier film is 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 to the analysis and research such as charge-discharge performance, cycle performance and high rate performance, result shows that its first discharge specific capacity is respectively 1402.6mAh/g, under the multiplying power of 1C and 2C, charge-discharge performance as shown in figure 12, 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 tri-
Be 20:1 by 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 5.60g particle diameter and be 60 μ m are that 200 order electrolytic copper powders and 6mL absolute ethyl alcohol are put into V-type drum mixer, rotating speed is 80r/min, and incorporation time is 4h, and the mixture of then getting 46mgNaCl and copper powder packs into and is of a size of Φ 12 × 0.34mm
3compacting tool set in, unidirectional be forced into 300MPa obtain blank.The above-mentioned blank making is placed in to tube furnace, under the protective atmosphere of argon gas, is warming up to 740 DEG C with the heating rate of 8 DEG C/min, temperature retention time is 3h, then, being warming up to 940 DEG C of insulation 1.5h, cools to room temperature with the furnace equally with the rate of temperature fall of 10 DEG C/min.Take out this sample and be placed in 50 DEG C of circulating hot water devices and remove molten NaCl particle, be then placed in baking oven 100 DEG C of oven dry, put into tube furnace after being cooled to room temperature, under protection argon gas atmosphere, be warming up to 250 DEG C with the speed of 10 DEG C/min, pass into H
2after reduction 1h, close H
2, pass into after argon gas is down to room temperature with stove is cooling and take out, making porosity is 70%, average pore size is the through-hole foam copper of 60 μ m.
Take respectively 0.145g six water nickel nitrates and 0.063g six water yttrium nitrates, dissolve in 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 foam copper sample, time is 1min, there is the foam copper of catalyst to take out load, then be placed at 90 DEG C of vacuum drying chambers after vacuumize 2h, put it in quartz boat, be placed in the constant temperature region, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield, rise to 200 DEG C of temperature with 10 DEG C/min of heating rate, calcining at constant temperature 4 hours, then rise to after 500 DEG C with 10 DEG C/min of heating rate crystal reaction tube, pass into hydrogen taking 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 DEG C of temperature with 5 DEG C/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas after 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, double helix carbon fiber combination electrode material obtains growing on foam copper matrix.
Taking the above-mentioned foam copper/double helix carbon fiber making as work electrode, taking metal lithium sheet as to electrode, barrier film is 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 to the analysis and research such as charge-discharge performance, cycle performance and high rate performance, result shows that its first discharge specific capacity is respectively 767.5mAh/g, under the multiplying power of 1C, after charge and discharge cycles 100 times, its specific discharge capacity is respectively 289.9mAh/g, has obtained good electro-chemical properties.
Embodiment tetra-
Be 10:1 by 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 9.64g particle diameter and be 90 μ m are that 200 order electrolytic copper powders and 8mL absolute ethyl alcohol are put into V-type drum mixer, rotating speed is 80r/min, and incorporation time is 1h, and the mixture of then getting 52mgNaCl and copper powder packs into and is of a size of Φ 12 × 0.46mm
3compacting tool set in, unidirectional be forced into 300MPa obtain blank.The above-mentioned blank making is placed in to tube furnace, under the protective atmosphere of argon gas, is warming up to 780 DEG C with the heating rate of 8 DEG C/min, temperature retention time is 1h, then, being warming up to 950 DEG C of insulation 3.5h, cools to room temperature with the furnace equally with the rate of temperature fall of 8 DEG C/min.Take out this sample and be placed in 100 DEG C of circulating hot water devices and remove molten NaCl particle, be then placed in baking oven 100 DEG C of oven dry, put into tube furnace after being cooled to room temperature, under protection argon gas atmosphere, be warming up to 250 DEG C with the speed of 8 DEG C/min, pass into H
2after reductase 12 h, close H
2, pass into after argon gas is down to room temperature with stove is cooling and take out, making porosity is 80%, average pore size is the through-hole foam copper of 90 μ m.
Take respectively 0.0029g six water nickel nitrates and 0.0013g six water yttrium nitrates, dissolve in 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 foam copper sample, time is 1min, there is the foam copper of catalyst to take out load, then be placed at 80 DEG C of vacuum drying chambers after vacuumize 4h, put it in quartz boat, be placed in the constant temperature region, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield, rise to 300 DEG C of temperature with 10 DEG C/min of heating rate, calcining at constant temperature 2 hours, then rise to after 400 DEG C with 3 DEG C/min of heating rate crystal reaction tube, pass into hydrogen taking 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 DEG C of temperature with 10 DEG C/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas after 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 foam copper matrix.
Taking the above-mentioned foam copper/noodles shape carbon fiber making as work electrode, taking metal lithium sheet as to electrode, barrier film is 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 8 and 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 to the analysis and research such as charge-discharge performance, cycle performance and high rate performance, result shows that its first discharge specific capacity is respectively 656.9mAh/g, under the multiplying power of 1C, after charge and discharge cycles 100 times, its specific discharge capacity is respectively 205.7mAh/g, has obtained good electro-chemical properties.
Embodiment five
Be 1:1 by 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 5.60g particle diameter and be 110 μ m are that 200 order electrolytic copper powders and 6mL absolute ethyl alcohol are put into V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 52mgNaCl and copper powder packs into and is of a size of Φ 12 × 0.54mm
3compacting tool set in, unidirectional be forced into 300MPa obtain blank.The above-mentioned blank making is placed in to tube furnace, under the protective atmosphere of argon gas, is warming up to 740 DEG C with the heating rate of 8 DEG C/min, temperature retention time is 3h, then, being warming up to 920 DEG C of insulation 3.5h, cools to room temperature with the furnace equally with the rate of temperature fall of 10 DEG C/min.Take out this sample and be placed in 60 DEG C of circulating hot water devices and remove molten NaCl particle, be then placed in baking oven 100 DEG C of oven dry, put into tube furnace after being cooled to room temperature, under protection argon gas atmosphere, be warming up to 250 DEG C with the speed of 8 DEG C/min, pass into H
2after reduction 1h, close H
2, pass into after argon gas is down to room temperature with stove is cooling and take out, making porosity is 70%, average pore size is the through-hole foam copper of 110 μ m.
Take respectively 0.029g six water nickel nitrates and 0.013g six water yttrium nitrates, dissolve in 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 foam copper sample, time is 10min, there is the foam copper of catalyst to take out load, then be placed at 90 DEG C of vacuum drying chambers after vacuumize 2h, put it in quartz boat, be placed in the constant temperature region, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield, rise to 300 DEG C of temperature with 10 DEG C/min of heating rate, calcining at constant temperature 3 hours, then rise to after 500 DEG C with 9 DEG C/min of heating rate crystal reaction tube, pass into hydrogen taking 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 DEG C of temperature with 10 DEG C/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas after 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, straight tube-like carbon fiber combination electrode material obtains growing on foam copper matrix.
Embodiment six
Be 10:1 by 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 5.60g particle diameter and be 80 μ m are that 200 order electrolytic copper powders and 7mL absolute ethyl alcohol are put into V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 60mgNaCl and copper powder packs into and is of a size of Φ 12 × 0.60mm
3compacting tool set in, unidirectional be forced into 300MPa obtain blank.The above-mentioned blank making is placed in to tube furnace, under the protective atmosphere of argon gas, is warming up to 760 DEG C with the heating rate of 8 DEG C/min, temperature retention time is 2h, then, being warming up to 930 DEG C of insulation 2.5h, cools to room temperature with the furnace equally with the rate of temperature fall of 8 DEG C/min.Take out this sample and be placed in 80 DEG C of circulating hot water devices and remove molten NaCl particle, be then placed in baking oven 100 DEG C of oven dry, put into tube furnace after being cooled to room temperature, under protection argon gas atmosphere, be warming up to 200 DEG C with the speed of 8 DEG C/min, pass into H
2after reduction 1.5h, close H
2, pass into after argon gas is down to room temperature with stove is cooling and take out, making porosity is 70%, average pore size is the through-hole foam copper of 80 μ m.
Take respectively 0.29g cobalt nitrate hexahydrate, dissolve in 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 foam copper sample, time is 20min, there is the foam copper of catalyst to take out load, then be placed at 100 DEG C of vacuum drying chambers after vacuumize 4h, put it in quartz boat, be placed in the constant temperature region, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield, rise to 400 DEG C of temperature with 8 DEG C/min of heating rate, calcining at constant temperature 4 hours, then rise to after 500 DEG C with 10 DEG C/min of heating rate crystal reaction tube, pass into hydrogen taking 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 DEG C of temperature with 10 DEG C/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas after 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, different-shape carbon fiber mixed structure combination electrode material obtains growing on foam copper matrix.
Embodiment seven
Be 20:1 by 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 9.64g particle diameter and be 60 μ m are that 200 order electrolytic copper powders and 8mL absolute ethyl alcohol are put into V-type drum mixer, rotating speed is 80r/min, and incorporation time is 2h, and the mixture of then getting 60mgNaCl and copper powder packs into and is of a size of Φ 12 × 0.60mm
3compacting tool set in, unidirectional be forced into 300MPa obtain blank.The above-mentioned blank making is placed in to tube furnace, under the protective atmosphere of argon gas, is warming up to 780 DEG C with the heating rate of 10 DEG C/min, temperature retention time is 1h, then, being warming up to 950 DEG C of insulation 1.5h, cools to room temperature with the furnace equally with the rate of temperature fall of 8 DEG C/min.Take out this sample and be placed in 100 DEG C of circulating hot water devices and remove molten NaCl particle, be then placed in baking oven 100 DEG C of oven dry, put into tube furnace after being cooled to room temperature, under protection argon gas atmosphere, be warming up to 400 DEG C with the speed of 10 DEG C/min, pass into H
2after reduction 1h, close H
2, pass into after argon gas is down to room temperature with stove is cooling and take out, making porosity is 80%, average pore size is the through-hole foam copper of 60 μ m.
Take respectively 0.29g cobalt nitrate hexahydrate, dissolve in 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 foam copper sample, time is 30min, there is the foam copper of catalyst to take out load, then be placed at 100 DEG C of vacuum drying chambers after vacuumize 1h, put it in quartz boat, be placed in the constant temperature region, middle part of quartz ampoule reacting furnace, pass into argon shield, under argon shield, rise to 400 DEG C of temperature with 10 DEG C/min of heating rate, calcining at constant temperature 1.5 hours, then rise to after 500 DEG C with 5 DEG C/min of heating rate crystal reaction tube, pass into hydrogen taking 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 DEG C of temperature with 10 DEG C/min of heating rate crystal reaction tube equally, the gaseous mixture that passes into a certain proportion of argon gas and acetylene gas after 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, different-shape carbon fiber mixed structure combination electrode material obtains growing on foam copper matrix.
Claims (1)
1. a preparation method for foam copper/carbon nanophase composite lithium ion battery cathode material, wherein 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) be 1:(1 ~ 20 by the NaCl particle of average grain diameter 0.5mm in ratio of grinding media to material), rotating speed is 100 ~ 500rpm, carries out ball milling under the condition that Ball-milling Time is 10 ~ 90min, obtaining particle diameter is the NaCl particle of 40 ~ 110 μ m;
(2) by step (1) process NaCl particle and 200 order electrolytic copper powders be 1:(0.24 ~ 1.37 according to mass ratio) and absolute ethyl alcohol put into V-type drum mixer, rotating speed is 80r/min, incorporation time is 1-4h, and the mixture of then getting NaCl and copper powder packs into and is of a size of Φ 12 × 0.34mm
3compacting tool set in, unidirectional be forced into 300MPa obtain blank;
(3) tube furnace that blank step (2) being made is placed in, pass into argon gas taking flow velocity as 150 ~ 300mL/min, be warming up to 740 ~ 780 DEG C of sintering 1 ~ 3h simultaneously taking heating rate as 3 ~ 10 DEG C/min, then be warming up to again 920 ~ 950 DEG C of sintering 1.5 ~ 3.5 h taking heating rate as 3 ~ 10 DEG C/min, through the naturally cooling sintering blank that obtains;
(4) by the sintering blank of step (3), the circulating hot water device that is placed in temperature and is 50 ~ 100 DEG C is molten except NaCl particle, in 50 ~ 100 DEG C of oven dry of temperature, the tube furnace being placed in again, passes into argon gas taking flow velocity as 150 ~ 300mL/min, and is warming up to 250 ~ 400 DEG C taking heating rate as 3 ~ 10 DEG C/min, pass into again after hydrogen 150 ~ 300mL/min reduction 1 ~ 3h, be down to room temperature, obtaining porosity is 50 ~ 85%, and aperture is the foam copper of 40 ~ 110 μ m;
2) Kaolinite Preparation of Catalyst presoma on foam copper matrix
(1) mol ratio of pressing nickel and yttrium is (1-2): 1, by nickel nitrate and yttrium nitrate, add in deionized water or 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 is added in deionized water or 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 of being prepared by step (1), time is 1-30min, through vacuumize 1 ~ 4h at 80 ~ 100 DEG C, obtaining load has the foam copper of catalyst, the foam copper of this supported catalyst is put into quartz boat, then quartz boat is placed on to the flat-temperature zone of tube furnace, under argon shield, be warming up to 200 ~ 400 DEG C with 3 ~ 10 DEG C/min of heating rate, calcining at constant temperature 1 ~ 4h, having obtained load has the foam copper matrix of catalyst precursor;
3) preparation of foam copper/carbon nanophase composite negative pole material
By step 2) load that makes has the foam copper matrix of catalyst precursor to be put in quartz boat, quartz boat is placed in to crystal reaction tube flat-temperature zone, under argon shield, be warming up to after 400 DEG C ~ 500 DEG C with 3 ~ 10 DEG C/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 argon shield, be warming up to 550 DEG C ~ 850 DEG C with 3 ~ 10 DEG C/min of heating rate, and be (10 ~ 50) by argon gas with acetylene gas volume ratio: 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, obtain foam copper/carbon nanophase composite lithium ion battery cathode material.
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| CN105742634A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院大连化学物理研究所 | Metal matrix carbon fiber felt |
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| CN104745853B (en) * | 2015-04-23 | 2017-01-18 | 苏州第一元素纳米技术有限公司 | Preparation method of foamed aluminum/ nano carbon composite material |
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| CN105695953B (en) * | 2016-01-19 | 2018-06-12 | 中国科学院化学研究所 | A kind of preparation method and application of three-dimensional carbon negative pole material |
| CN106098401B (en) * | 2016-07-08 | 2018-06-08 | 武汉工程大学 | A kind of preparation method of carbon copper-clad combination electrode material |
| CN106400062B (en) * | 2016-12-01 | 2018-07-31 | 贵州木易精细陶瓷有限责任公司 | Copper carbon composite and preparation method thereof and device |
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| CN114606521B (en) * | 2022-03-01 | 2023-11-10 | 西北工业大学 | Copper foam electrode modified by phytic acid and application of copper foam electrode in preparing aniline by electrocatalytic reduction of nitrobenzene |
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