CN102394305B - Foamy copper oxide/copper lithium ion battery anode and preparation method thereof - Google Patents
Foamy copper oxide/copper lithium ion battery anode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a foamy copper oxide/copper lithium ion battery anode and a preparation process thereof, and the process comprises the following steps: performing surface pickling treatment of foamy copper, cleaning with water, stoving, performing compacting treatment; performing surface oxidation treatment in a heat treatment furnace with air atmosphere to obtain a layer of copper oxides (CuO, Cu2O, or a mixture of the two) on the surface; mixing a carbon-based conductive agent, a binder, and a solvent to obtain slurry, coating the slurry on the surface of the foamy copper oxide/copper composite material, stoving and compacting. The copper oxide/copper material which is coated with the conductive agent and the binder and has a three dimensional structure can be directly used as an anode of a lithium ion battery, and no processes for preparing slurry by the active substance, the binder, and the conductive agent and coating the slurry on a current collector, which are required for traditionally preparing a lithium ion battery anode, are required. The coated conductive agent and binder can increase the electrical contact of the copper oxide active substance during the charge and discharge processes, and increase the electron conductivity and the utilization rate of the active substance. The lithium ion battery anode of the invention has high specific capacity, and good cycle performance; the preparation method of the electrode is simple and easily controlled, and is quite applicable to industrial application of lithium ion batteries.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly a kind of lithium ion battery negative and preparation method thereof.
Background technology
Lithium ion battery has that operating voltage is high, specific capacity is high, memory-less effect, advantages of environment protection, since coming out, has been widely used in the portable electric appts such as mobile phone, notebook computer, miniature camera.Along with the day by day increase of modern society to energy demand, limited deposit and the day by day raising of human society to environmental requirement of tradition fossil energy, the demand of the green secondary power supply of the high-energy-density such as deposit, electric tool to electric automobile, electric bicycle, solar energy and wind energy and high power density and good serviceability is day by day urgent, lithium ion battery has the potentiality that meet its requirement, and the research and development of high-performance electrode and electrode material is the key that improves performance of lithium ion battery.
Commercial li-ion battery is mainly taking graphitization carbon back as negative material at present, but its theoretical lithium storage content is only 372 mAh/g, the capacity of commercial carbon negative pole has approached its theoretical capacity very much, very little with the potentiality of raising battery performance to its further exploitation.Therefore existing carbon negative pole material is difficult to meet the lithium ion battery requirement of high power capacity, high power density.In recent years, the research and development of high power capacity negative material is subject to various countries researcher's extensive attention, and wherein more typical material has two classes: it is 4200 mAh/g that a class is mainly its theoretical capacity of simple substance Si() and its theoretical capacity of Sn(be 992 mAh/g); Another kind of for transition metal oxide MO(wherein M be Fe, Cu, Ni etc.) and metal oxide as SnO
2deng.But the negative material ubiquity of these high power capacity is irreversible capacity height and the poor problem of cyclical stability first.In above-mentioned negative material, the theoretical capacity of CuO is 674 mAh/g, is 2 times of left and right of commercial carbon negative pole material, Cu
2the theoretical capacity of O is 372 mAh/g.But CuO and Cu
2the density of O is three times of left and right of carbon-based material, thereby has larger volume storage lithium density, and its nontoxic, easily storage, thereby it has development potentiality and application prospect as lithium ion battery negative material, Cu oxide (CuO, Cu
2o or both mixtures) just constantly come into one's own for the research of lithium ion battery negative material.But then, the major defect that Cu oxide exists as lithium ion battery negative material is because its volumetric expansion in embedding lithium process can reach more than 150%, causes material efflorescence serious, adds CuO, Cu
2o is semiconductor, and its electronic conductivity is low, thereby makes part active material lose effectively and electrically contact in cyclic process, has reduced specific capacity and the cycle performance of battery.Therefore, need to be to CuO, Cu
2o material carries out modification, is keeping, under the condition of its high capacity characteristics, improving its cyclical stability.Conventional method mainly contains nanometer, compound and prepare membrane electrode etc.
At present, commercial production lithium ion battery all comprises loaded down with trivial details both positive and negative polarity preparation process.In the production process of negative pole, first negative electrode active material, binding agent, conductive agent and solvent to be made to slurry by certain proportioning, then slurry is coated in to negative current collector copper foil surface by painting process.In the process of preparing slurry, need active material and conductive agent and binding agent evenly to mix, otherwise can cause that active material applies problem inhomogeneous and that peel off, makes the difficult quality control of negative pole.Thereby in actual production, hope can be found a kind of negative pole of high power capacity and good circulation stability and preparation method that preparation technology's flow process is simple, production cost is low thereof of having concurrently.
Chinese patent CN102013470A discloses one taking foam copper, iron, nickel as raw material, generates corresponding oxide by oxidation reaction original position, thereby is directly used as the negative pole of lithium ion battery.But because the conductivity of oxide is poor, and it easily produces efflorescence and peels off from copper matrix because volume changes a lot in removal lithium embedded process, thereby the electric conductivity of material is further declined, and the utilance of active material declines, the capacity of electrode and cycle performance are declined.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Foamy copper oxide/copper lithium ion battery anode, the collector of this negative pole is that porosity is 50 ~ 85% foam copper, described collector foam copper surface in situ growth has the Cu oxide of stratiform, and the thickness of described layered copper oxide is 200 nm ~ 2 μ m.Described Cu oxide can be CuO or Cu
2o or both mixtures, described foam copper oxide/copper negative pole has three-dimensional structure, and this negative pole has good cyclical stability and high specific capacity.
The present invention also provides the method for preparing this Foamy copper oxide/copper lithium ion battery anode, taking foam copper as collector and the raw material of active material, by foam copper being carried out in the heat-treatment furnace of air atmosphere to the oxidation of different temperatures and time, at the Cu oxide of foam copper Surface Creation stratiform, this Cu oxide can be CuO or Cu
2o or both mixtures.By controlling different oxidizing temperatures and time, can obtain the layered copper oxide with variety classes, thickness, different-shape.Cu oxide layer is combined closely with copper matrix, and by subsequently in foam copper oxide/copper surface-coated containing carbon-based conductive agent and binding agent, drying and compacting, obtaining surface-coated has skim to contain the foam copper oxide/copper product of carbon-based conductive agent and binding agent, and this material can directly be used as lithium ion battery negative.
The present invention is by applying or dipping conductive agent and binding agent on the foam copper oxide/copper product there is layered copper oxide through the surface in situ growth of air oxidation with foam copper, and drying appropriate compacting can be used for lithium ion battery negative after processing.The introducing of conductive agent and binding agent, increase Cu oxide electrically contacting in electrode charge and discharge process, strengthen the conductivity of electrode, improved the utilance of active material, made foam copper oxide/copper negative pole there is high specific discharge capacity and good cyclical stability.The preparation method of this lithium ion battery negative is simple, and cost is low, is applicable to large-scale production, has business-like application prospect.
The method that the present invention prepares Foamy copper oxide/copper lithium ion battery anode is: first by thermal oxidation method at collector foam copper surface in situ growth layered copper oxide, the then coating containing carbon-based conductive agent and binding agent in foam copper oxide/copper surface-coated.
Method at collector foam copper surface in situ growth layered copper oxide active material of the present invention comprises the steps:
(1) foam copper is carried out to surface acid-washing processing, then water cleans and dries;
(2) foam copper after cleaning, drying is carried out to compaction treatment under 2 ~ 20 MPa pressure;
(3) foam copper after compaction treatment is placed in to heat-treatment furnace, be warming up to 200 ~ 600 ° of C, in air atmosphere, carry out thermal oxidative reaction, be incubated 0.25 ~ 20 hour, at foam copper surface in situ growth layered copper oxide, obtain foam copper oxide/copper product, be then cooled to room temperature.
Wherein, the porosity of described foam copper is 50 ~ 85%, and described Cu oxide is CuO or Cu
2o or both mixtures, the thickness of described epontic layered copper oxide is 200 nm ~ 2 μ m, and described acid is hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid or nitric acid, and its molar concentration is 0.05 ~ 2 mol/L.
Method at foam copper oxide/copper surface-coated conductive agent and binding agent of the present invention comprises the steps:
(1) by conductive agent, binding agent and solvent, the ratio taking mass ratio as 1:0.5 ~ 2:10 ~ 100 is made into slurry;
(2) slurry is coated in to the surface of foam copper oxide/copper product, or foam copper oxide/copper be impregnated in slurry, then propose, drain slurry;
(3) dry the foam copper oxide/copper product being coated with containing carbon-based conductive agent and binding agent slurry, and adopt the pressure of 10 ~ 20 MPa to be pressed into thin slice to it, the foam copper oxide/copper product making can directly be used as the negative pole of lithium ion battery.
Wherein, described is one or any mixture of acetylene black, carbon black or Graphene containing carbon-based conductive agent, and described binding agent is polyvinylidene fluoride or sodium carboxymethylcellulose, and described solvent is 1-METHYLPYRROLIDONE.
As preferably, the quality of conductive agent and binding agent accounts for 10 ~ 30% of active material Cu oxide quality, and conductive agent and binding agent account for the size of active material Cu oxide amount by the addition control of solvent.Amount of solvent is more, and slurry is rarer, and the conductive agent that unit Cu oxide scale face contains and the amount of binding agent are fewer.
Beneficial effect of the present invention is as follows:
(1) ensured contact and bond strength good between Cu oxide and copper matrix according to the present invention in the method for collector foam copper surface in situ oxidation growth Cu oxide layer, using it as lithium ion battery negative, the utilance of active material is high.
(2) the present invention, by make the kind of Cu oxide and thickness controllable to the control of oxidizing temperature and time, can obtain Cu on foam copper surface by low-temperature oxidation
2o or with Cu
2o is main Cu
2o/CuO mixture layer; Cu
2the specific capacity of O is low with respect to CuO, makes electrode in charge and discharge cycles process, have stronger productive technique, is conducive to improve the stability of electrode charge and discharge circulation; And under higher oxidizing temperature, obtain taking CuO as main Cu
2o/CuO mixture layer or CuO layer, high-temperature oxydation speed is fast, and can obtain desired thickness by the oxidation of short period is the Cu oxide layer of active matter quality, enhances productivity, and the specific discharge capacity of CuO is high, can obtain the electrode of high power capacity.
(3) the present invention is at a certain amount of conductive agent of foam copper oxide/copper surface-coated and binding agent, increase the conductivity of Cu oxide layer, make the Cu oxide particle of efflorescence in charge and discharge cycles process keep electrically contacting preferably, improve the conductivity of Cu oxide active material, further improved the utilance of active material; This superficial growth has Cu oxide and is coated with conductive agent and the foam copper of binding agent can be directly used in the negative pole of lithium ion battery, and has high discharge capacity and good cycle performance.
(4) method of preparing lithium ion battery negative provided by the invention has been saved mixing and the coating of active material and conductive agent and binding agent, and the coating of binding agent and conductive agent is relatively simple; Foam copper oxide/copper negative pole prepared by the present invention has three-dimensional structure, and active material specific area is large, and the contact-making surface of electrolyte and active material is large, and the migration of lithium ion and diffusion are easily.This structure has been alleviated the strain that Cu oxide produces due to change in volume in removal lithium embedded process simultaneously, has reduced the efflorescence of Cu oxide, and this negative pole has high power capacity and good dynamic performance.
(5) preparation method of lithium ion battery negative of the present invention, technique is simple, is suitable for commercially producing, and has larger commercial application prospect.
Brief description of the drawings
Fig. 1 is the surface-coated conductive agent prepared of embodiment 1 and the foam CuO/Cu of binding agent
2the uncoated conductive agent in surface of 1 preparation and the foam CuO/Cu of binding agent are implemented in O/Cu negative pole and employing
2the cycle performance comparison diagram of O/Cu negative pole;
Fig. 2 is foam Cu prepared by embodiment 2
2eSEM (SEM) pattern of the surface of O/CuO/Cu material under different amplification, (a) figure has shown foam Cu
2the three-dimensional structure of O/CuO/Cu material, (b) figure shows the Cu oxide pattern of this material surface;
Fig. 3 is the surface-coated conductive agent prepared of embodiment 2 and the foam Cu of binding agent
2the cycle performance figure of O/CuO/Cu negative pole;
Fig. 4 is the surface-coated conductive agent prepared of embodiment 3 and the foam Cu of binding agent
2the cycle performance figure of O/Cu negative pole;
Fig. 5 is the surface-coated conductive agent prepared of embodiment 5 and the foam CuO/Cu of binding agent
2the X-ray diffracting spectrum of O/Cu material;
Fig. 6 is the surface-coated conductive agent prepared of embodiment 5 and the foam CuO/Cu of binding agent
2the cycle performance figure of O/Cu negative pole.
Embodiment
The present invention may be better understood for following examples, but the present invention is not limited to following examples.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
embodiment 1
The foam copper that is 70% by porosity carries out surface acid processing with the hydrochloric acid of 1mol/L to it, then water cleans post-drying; Foam copper after drying is carried out to compaction treatment under 8 MPa pressure, the foam copper after compaction treatment is placed in to heat-treatment furnace, be warming up to 400 ° of C, in air atmosphere, carry out thermal oxidative reaction, be incubated 0.25 hour, be then cooled to room temperature.It is the micro Cu that contains taking CuO as leading of 400 nm at foam copper surface in situ growth thickness
2the layered copper oxide of O, obtains foam CuO/Cu
2o/Cu material.
By conductive agent carbon black, binding agent PVDF(polyvinylidene fluoride), solvent NMP(N-methyl pyrrolidone) be mixed with slurry with the mass ratio of 1:1:100, stir.By the above-mentioned foam CuO/Cu making
2o/Cu material immerses in slurry, subsequently its proposition is drained to unnecessary slurry, dries, then is pressed into thin slice with the pressure of 15 MPa, can be used as lithium ion battery negative.
The test of electrode electro Chemical performance adopts CR2025 type button simulated battery to test.By the foam CuO/Cu of the uncoated conductive agent in the above-mentioned surface making and binding agent
2the foam CuO/Cu of O/Cu material and surface-coated conductive agent and binding agent
2o/Cu material is cut into the disk of required size, using lithium sheet (purity >99.9%) as to electrode, PE monofilm (ENTEK) is barrier film, and electrolyte is the mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC) of 1 mol/L LiPF6.Battery pack is contained in the LABSTAR glove box that German MBRAUN company produces and completes, and is full of high-purity argon gas, H in glove box
2o, O
2content is all less than 0.1 ppm, finally in glove box, utilizes sealing machine to seal.
Adopt Land battery test system (specification 5V, 2mA) to carry out constant current charge-discharge test to assembled simulated battery.Charging and discharging currents is 67 mA/g, and voltage range is 0.02-2.5 V.The present invention's active material quality used in the time calculating charging and discharging capacity does not comprise foam CuO/Cu
2the quality of the contained body Cu that dams in O/Cu material.Electrochemical property test demonstration, different in the continuous decline of cyclic process capacity from general oxide cathode material, this surface-coated has the foam CuO/Cu of conductive agent and binding agent
2o/Cu material is as lithium ion battery negative, and the loss of capacity only appears at after electric discharge first, and in cyclic process, specific discharge capacity constantly increases, and reversible capacity is 230 mAh/g first, after 40 circulations, reaches 330 mAh/g.The long service life of electrode, capacity is high.
The foam CuO/Cu of surface-coated prepared by the present embodiment and uncoated conductive agent and binding agent
2fig. 1 is shown in the contrast of the chemical property of O/Cu lithium ion battery negative.The foam CuO/Cu of uncoated conductive agent and binding agent than surface as seen from Figure 1
2o/Cu electrode, the capacity of negative plates of coated with conductive agent and binding agent is improved significantly.
embodiment 2
The foam copper that is 50% by porosity carries out surface acid processing with the nitric acid of 0.05 mol/L to it, then water cleans post-drying; Foam copper after drying is carried out to compaction treatment under 20 MPa pressure, foam copper after compaction treatment is placed in to heat-treatment furnace, is warming up to 250 ° of C, in air atmosphere, carry out thermal oxidative reaction, be incubated 4 hours, foam copper surface in situ growth thickness be 200 nm with Cu
2o is main, and contains the stratiform foam Cu of micro Cu O
2o/CuO oxide, obtains foam Cu
2o/CuO/Cu material, is then cooled to room temperature.
By conductive agent acetylene black, binding agent PVDF(polyvinylidene fluoride), solvent NMP(N-methyl pyrrolidone) be mixed with slurry with the mass ratio of 1:0.5:10, stir.By slurry brushing at the above-mentioned foam Cu making
2o/CuO/Cu material surface, then dries, then is pressed into thin slice with the pressure of 20 MPa, obtains lithium ion battery negative.
The foam Cu making
2the scanning electron microscope (SEM) photograph (SEM) of the surface of O/CuO/Cu material under different amplification is shown in Fig. 2, and wherein figure (a) has shown this foam Cu
2the three-dimensional structure pattern of O/CuO/Cu material, in figure, visible this material surface is without peeling off and crackle, and copper oxide is combined well with copper substrate; Figure (b) shows the pattern of the Cu oxide of this material surface, and in figure, visible this material list face length has graininess Cu oxide.
Adopt the method identical with embodiment 1 to prepare CR2025 type button simulated battery, and assembled simulated battery is carried out to constant current charge-discharge test, its cycle performance is shown in Fig. 3.Negative pole prepared by the present embodiment is after circulation first, and capacity no longer declines, and shows higher capacity and good cyclical stability.Reversible capacity is 352 mAh/g first, and specific discharge capacity constantly rises in cyclic process, reaches 442 mAh/g, apparently higher than the theoretical capacity of business carbon negative pole after 40 circulations.Because the capacity of negative pole in cyclic process constantly increases, electrode life is long, and capacity is high.
embodiment 3
The foam copper that is 85% by porosity carries out surface acid processing with the acetic acid of 2 mol/L to it, then water cleans post-drying; Foam copper after drying is carried out to compaction treatment under 2 MPa pressure, foam copper after compaction treatment is placed in to heat-treatment furnace, is warming up to 200 ° of C, in air atmosphere, carry out thermal oxidative reaction, being incubated 20 hours, is the stratiform Cu of 600 nm at foam copper surface in situ growth thickness
2o, obtains foam Cu
2o/Cu material, is then cooled to room temperature.
The mixture of the conductive agent acetylene black that is 7:3 by mass ratio and carbon black, binding agent PVDF(polyvinylidene fluoride), solvent NMP(N-methyl pyrrolidone) be mixed with slurry with 1:2:100, stir.By the above-mentioned foam Cu making
2o/Cu material immerses in slurry, subsequently its proposition is drained to unnecessary slurry, dries, then is pressed into thin slice with the pressure of 18 MPa, obtains lithium ion battery negative.
Adopt the method identical with embodiment 1 to prepare CR2025 type button simulated battery, and assembled simulated battery is carried out to constant current charge-discharge test, negative pole prepared by the present embodiment is after electric discharge first, and capacity no longer declines, and shows good cyclical stability.The long service life of electrode, capacity is high.Reversible capacity is 220 mAh/g first, and after 60 circulations, Capacitance reserve is 310 mAh/g, and its cycle performance is shown in Fig. 4.
embodiment 4
The foam copper that is 60% by porosity carries out surface acid processing with the phosphoric acid of 1 mol/L to it, then water cleans post-drying; Foam copper after drying is carried out to compaction treatment under 10 MPa pressure, foam copper after compaction treatment is placed in to heat-treatment furnace, be warming up to 600 ° of C, in air atmosphere, carry out thermal oxidative reaction, be incubated 5 hours, be the stratiform CuO of 2 μ m at foam copper surface in situ growth thickness, obtain foam CuO/Cu material, be then cooled to room temperature.
The conductive agent acetylene black that is 8:2 by mass ratio and Graphene mixture, binding agent CMC(sodium carboxymethylcellulose),, solvent NMP(N-methyl pyrrolidone) be mixed with slurry with the mass ratio of 1:1:40, stir.Slurry brushing, at the above-mentioned foam CuO/Cu material surface making, after oven dry, then is pressed into thin slice with the pressure of 10 MPa, obtains lithium ion cell electrode.
Adopt the method identical with embodiment 1 to prepare CR2025 type button simulated battery, and assembled simulated battery is carried out to constant current charge-discharge test, negative pole prepared by the present embodiment shows good cyclical stability, reversible capacity is 180 mAh/g first, and after 60 circulations, Capacitance reserve is 260 mAh/g.Capacity constantly increases in cyclic process, the long service life of negative pole.
embodiment 5
The foam copper that is 60% by porosity carries out surface acid processing with the sulfuric acid of 0.05 mol/L to it, then water cleans post-drying; Foam copper after drying is carried out to compaction treatment under 10MPa pressure, foam copper after compaction treatment is placed in to heat-treatment furnace, is warming up to 350 ° of C, in air atmosphere, carry out thermal oxidative reaction, be incubated 5 hours, foam copper surface in situ growth thickness be 700 nm with CuO for a small amount of Cu that advocates peace
2the stratiform CuO/Cu of O
2o compound, obtains foam CuO/Cu
2o/Cu material, is then cooled to room temperature.The X-ray diffracting spectrum of this material is shown in Fig. 5, and in figure, the Cu oxide layer on visible foam copper surface includes CuO and Cu
2o.
By conductive agent Graphene, binding agent CMC(sodium carboxymethylcellulose), solvent NMP(N-methyl pyrrolidone) be mixed with slurry with the mass ratio of 1:1:80, stir.The above-mentioned foam CuO/Cu making is immersed in slurry, subsequently its proposition is drained to unnecessary slurry, dry, then be pressed into thin slice with the pressure of 20 MPa, obtain lithium ion cell electrode.
Adopt the method identical with embodiment 1 to prepare CR2025 type button simulated battery, and assembled simulated battery is carried out to constant current charge-discharge test, negative pole prepared by the present embodiment capacity after discharging first does not decline, and shows good cyclical stability.In cyclic process, capacity of negative plates constantly increases, the long service life of negative pole, and capacity is high.Reversible capacity is 250 mAh/g first, and after 60 circulations, Capacitance reserve is 330 mAh/g, and its cycle performance is shown in Fig. 6.
Claims (8)
1. a Foamy copper oxide/copper lithium ion battery anode, it is characterized in that: collector is that porosity is 50～85% foam copper, described collector foam copper surface in situ growth has the Cu oxide of stratiform, there are conductive agent and binding agent in its surface-coated again, described conductive agent is for containing carbon-based conductive agent, described is acetylene black containing carbon-based conductive agent, the one of carbon black or Graphene or any mixture, described binding agent is polyvinylidene fluoride or sodium carboxymethylcellulose, described conductive agent and the quality of binding agent account for 10～30% of active material Cu oxide quality, the thickness of described layered copper oxide is 200nm～2 μ m, described foam copper oxide/copper negative pole has three-dimensional structure.
2. Foamy copper oxide/copper lithium ion battery anode according to claim 1, is characterized in that: described Cu oxide is CuO, Cu
2o or both mixtures.
3. the method for preparation Foamy copper oxide/copper lithium ion battery anode as claimed in claim 1, it is characterized in that: by thermal oxidation method at collector foam copper surface in situ growth layered copper oxide, then the coating containing carbon-based conductive agent and binding agent in foam copper oxide/copper surface-coated, described conductive agent is for containing carbon-based conductive agent, described is acetylene black containing carbon-based conductive agent, the one of carbon black or Graphene or any mixture, described binding agent is polyvinylidene fluoride or sodium carboxymethylcellulose, described conductive agent and the quality of binding agent account for 10～30% of active material Cu oxide quality.
4. the method for preparing Foamy copper oxide/copper lithium ion battery anode according to claim 3, comprises the steps:
(1) foam copper is carried out to surface acid-washing processing, then water cleans and dries;
(2) foam copper after drying is carried out to compaction treatment under 2～20MPa pressure;
(3) foam copper after compaction treatment is placed in to heat-treatment furnace, be warming up to 200～600 DEG C, in air atmosphere, carry out thermal oxidative reaction, be incubated 0.25～20 hour, at foam copper surface in situ growth layered copper oxide, obtain foam copper oxide/copper product, be then cooled to room temperature;
(4) will be mixed with slurry containing carbon-based conductive agent, binding agent and solvent, at above-mentioned foam copper oxide/copper product surface-coated slurry, then by its oven dry;
(5) surface after drying is scribbled containing the foam copper oxide/copper product of carbon-based conductive agent and binding agent and presses down and laminate at 10～20MPa pressure, obtain Foamy copper oxide/copper lithium ion battery anode.
5. the method for preparing Foamy copper oxide/copper lithium ion battery anode according to claim 4, is characterized in that: described Cu oxide is CuO, Cu
2o or both mixtures, the thickness of described epontic layered copper oxide is 200nm～2 μ m.
6. the method for preparing Foamy copper oxide/copper lithium ion battery anode according to claim 4, is characterized in that: the acid described in step (1) is hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid or nitric acid, and its molar concentration is 0.05～2mol/L.
7. the method for preparing Foamy copper oxide/copper lithium ion battery anode according to claim 4, it is characterized in that: described in step (4) is one or any mixture of acetylene black, carbon black or Graphene containing carbon-based conductive agent, described binding agent is polyvinylidene fluoride or sodium carboxymethylcellulose, and described solvent is 1-METHYLPYRROLIDONE.
8. the method for preparing Foamy copper oxide/copper lithium ion battery anode according to claim 4, is characterized in that: the mass ratio containing carbon-based conductive agent, binding agent and solvent described in step (4) is 1: 0.5～2: 10～100.
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