CN102394305A - 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
- Publication number
- CN102394305A CN102394305A CN2011103910541A CN201110391054A CN102394305A CN 102394305 A CN102394305 A CN 102394305A CN 2011103910541 A CN2011103910541 A CN 2011103910541A CN 201110391054 A CN201110391054 A CN 201110391054A CN 102394305 A CN102394305 A CN 102394305A
- Authority
- CN
- China
- Prior art keywords
- copper
- oxide
- lithium ion
- ion battery
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 operating voltage height, specific capacity height, 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; Deposit that the tradition fossil energy is limited and human society are to the raising day by day of environmental requirement; Increasing demand to the green secondary power supply of high-energy-density such as the deposit of electric automobile, electric bicycle, solar energy and wind energy, electric tool and high power density and good serviceability is urgent; Lithium ion battery has the potentiality that satisfy its requirement, and the research and development of high-performance electrode and electrode material is the key that improves the lithium ion battery performance.
The commercial li-ion battery is a negative material with the graphitization carbon back mainly at present; But its theoretical lithium storage content is merely 372 mAh/g; The capacity of commercial carbon negative pole is very near its theoretical capacity, and is very little with the potentiality that improve battery performance to its further exploitation.Therefore existing carbon negative pole material is difficult to satisfy 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 receives various countries researcher's extensive attention, wherein has two types than exemplary material: one type is mainly simple substance Si (its theoretical capacity is 4200 mAh/g) and Sn (its theoretical capacity is 992 mAh/g); Another kind of is transition metal oxide MO (wherein M is Fe, Cu, Ni etc.) and metal oxide such as SnO
2Deng.But the negative material ubiquity of these high power capacity is the problem of the high and cyclical stability difference of irreversible capacity first.In above-mentioned negative material, the theoretical capacity of CuO is 674 mAh/g, is about 2 times 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 about three times of carbon-based material, thereby has bigger volume storage lithium density, and its nontoxic, easy storage, thereby it has development potentiality and application prospect as lithium ion battery negative material, Cu oxide (CuO, Cu
2O or both mixtures) research that is used for lithium ion battery negative material just constantly comes into one's own.But then, the major defect that Cu oxide exists as lithium ion battery negative material is owing to its volumetric expansion in the embedding lithium process can reach more than 150%, causes the material efflorescence serious, adds CuO, Cu
2O is a semiconductor, and its electronic conductivity is low, electrically contacts thereby the part active material is lost effectively in cyclic process, has reduced the specific capacity and the cycle performance of battery.Therefore, need be to CuO, Cu
2The O material carries out modification, under the condition that keeps its high capacity characteristics, improves its cyclical stability.Method commonly used mainly contains nanometerization, compound and preparation membrane electrode etc.
At present, the commercial production lithium ion battery comprises that all loaded down with trivial details both positive and negative polarity prepares process.In the production process of negative pole, at first to negative electrode active material, binding agent, conductive agent and solvent be processed slurry by certain proportioning, then slurry is coated in the negative current collector copper foil surface through painting process.In the process of preparation slurry, need active material and conductive agent and binding agent evenly be mixed, otherwise can cause that active material applies inhomogeneous and the problem of peeling off, and makes the difficult quality of negative pole control.Thereby in actual production, hope can be found a kind of high power capacity and the negative pole of good circulation stability and preparation method that preparation technology's flow process is simple, production cost is low thereof of having concurrently.
It is raw material with foam copper, iron, nickel that Chinese patent CN102013470A discloses a kind of, generates corresponding oxide through the oxidation reaction original position, thereby directly is used as the negative pole of lithium ion battery.But because the conductivity of oxide is relatively poor; And it is prone to produce efflorescence and peel off from the copper matrix owing to volume changes a lot in the removal lithium embedded process; Thereby the electric conductivity of material is further descended, and the utilance of active material descends, and the capacity of electrode and cycle performance are descended.
Summary of the invention
Deficiency to prior art; The present invention provides a kind of foam copper oxide/copper lithium ion battery negative; 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 foam copper oxide/copper lithium ion battery negative; With the foam copper is the raw material of collector and active material; Through foam copper is carried out the oxidation of different temperatures and time in the heat-treatment furnace of air atmosphere; Generate the Cu oxide of stratiform on the foam copper surface, this Cu oxide can be CuO or Cu
2O or both mixtures.Through control different oxidation temperature and time, can obtain to have the layered copper oxide of variety classes, thickness, different-shape.Cu oxide layer and copper matrix bond are tight; And through subsequently contain carbon back conductive agent and binding agent in foam copper oxide/copper surface-coated; Through oven dry and compacting; Obtain surfaces coated and be covered with foam copper oxide/copper product that skim contains carbon back conductive agent and binding agent, this material can directly be used as lithium ion battery negative.
The present invention after oven dry and appropriate compacting processing, promptly can be used for lithium ion battery negative through on foam copper oxide/copper product that layered copper oxide is arranged through the growth of the surface in situ of air oxidation with foam copper, applying or dipping conductive agent and binding agent.The introducing of conductive agent and binding agent; Increased Cu oxide electrically contacting in electrode charge and discharge process; Strengthened the conductivity of electrode, improved the utilance of active material, made foam copper oxide/copper negative pole have high specific discharge capacity and good cyclical stability.The preparation method of this lithium ion battery negative is simple, and cost is low, is fit to large-scale production, has business-like application prospect.
The method that the present invention prepares foam copper oxide/copper lithium ion battery negative is: at first pass through thermal oxidation method at collector foam copper surface in situ growth layered copper oxide, contain the coating of carbon back conductive agent and binding agent in foam copper oxide/copper surface-coated then.
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 surface acid-washing and handle, water cleans and oven dry again;
(2) foam copper behind the cleaning, drying is carried out compaction treatment under 2 ~ 20 MPa pressure;
(3) foam copper after compaction treatment is placed 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 cooled to room temperature then.
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 are 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) be that the ratio of 1:0.5 ~ 2:10 ~ 100 is made into slurry with the mass ratio with conductive agent, binding agent and solvent;
(2) slurry is coated in the surface of foam copper oxide/copper product, or foam copper oxide/copper impregnated in the slurry, propose then, drain slurry;
(3) oven dry is coated with the foam copper oxide/copper product that contains carbon back conductive agent and binding agent slurry, and adopts the pressure of 10 ~ 20 MPa to be pressed into thin slice to it, and the foam copper oxide/copper product that makes can directly be used as the negative pole of lithium ion battery.
Wherein, describedly contain a kind of or any mixture that the carbon back conductive agent is acetylene black, carbon black or Graphene, described binding agent is polyvinylidene fluoride or sodium carboxymethylcellulose, and described solvent is the N-methyl pyrrolidone.
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 addition control of the size of active material Cu oxide amount by solvent.Amount of solvent is many more, and slurry is rare more, and the conductive agent that unit Cu oxide scale face contains and the amount of binding agent are few more.
Beneficial effect of the present invention is following:
(1) guaranteed excellent contact and bond strength between Cu oxide and the copper matrix according to the present invention in the method for collector foam copper surface in situ oxidation growth Cu oxide layer, as lithium ion battery negative, the utilance of active material is high with it.
(2) the present invention makes the kind of Cu oxide and controllable thickness adjustable through the control to oxidizing temperature and time, can obtain Cu on the foam copper surface through low-temperature oxidation
2O or with Cu
2O is main Cu
2The O/CuO mixture layer; Cu
2The specific capacity of O is low with respect to CuO, makes electrode in the charge and discharge cycles process, have stronger anti-efflorescence ability, helps improving the electrode charge and discharge cycle stability; And under higher oxidizing temperature, obtaining with CuO is main Cu
2O/CuO mixture layer or CuO layer, high-temperature oxydation speed is fast, and can obtain desired thickness through 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 foam copper oxide/a certain amount of conductive agent of copper surface-coated and binding agent; Increased the conductivity of Cu oxide layer; Make the Cu oxide particle of efflorescence in the 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 directly be used for the negative pole of lithium ion battery, and has high discharge capacity and excellent cycle performance.
(4) method for preparing lithium ion battery negative provided by the invention has been saved the mixing and the coating of active material and conductive agent and binding agent, and the coating of binding agent and conductive agent is simpler relatively; Foam copper oxide/copper the negative pole of the present invention's preparation has three-dimensional structure, and the active material specific area is big, and the contact-making surface of electrolyte and active material is big, and the migration of lithium ion and diffusion are easily.This structure has been alleviated the strain that Cu oxide produces owing to change in volume in the 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, technology is simple, is suitable for commercially producing, and has bigger commercial application prospect.
Description of drawings
Fig. 1 is the surface-coated conductive agent of embodiment 1 preparation and the foam CuO/Cu of binding agent
2O/Cu negative pole and the surperficial uncoated conductive agent that adopts enforcement 1 preparation and the foam CuO/Cu of binding agent
2The cycle performance comparison diagram of O/Cu negative pole;
Fig. 2 is the foam Cu of embodiment 2 preparations
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 of embodiment 2 preparations 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 of embodiment 3 preparations and the foam Cu of binding agent
2The cycle performance figure of O/Cu negative pole;
Fig. 5 is the surface-coated conductive agent of embodiment 5 preparations 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 of embodiment 5 preparations and the foam CuO/Cu of binding agent
2The cycle performance figure of O/Cu negative pole.
Embodiment
Following examples can be understood the present invention better, but the present invention is not limited to following examples.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
To be 70% foam copper with porosity carry out surface acid with the hydrochloric acid of 1mol/L to it handles, and water cleans the back oven dry again; Foam copper after the oven dry is carried out compaction treatment under 8 MPa pressure, the foam copper after the compaction treatment is placed heat-treatment furnace, be warming up to 400 ° of C, in air atmosphere, carry out thermal oxidative reaction, be incubated 0.25 hour, be cooled to room temperature then.Foam copper surface in situ growth thickness be 400 nm be the main micro Cu that contains with CuO
2The layered copper oxide of O obtains foam CuO/Cu
2The O/Cu material.
Conductive agent carbon black, binding agent PVDF (polyvinylidene fluoride), solvent NMP (N-methyl pyrrolidone) are mixed with slurry with the mass ratio of 1:1:100, stir.With the above-mentioned foam CuO/Cu that makes
2The O/Cu material immerses in the slurry, subsequently its proposition is drained unnecessary slurry, oven dry, and the pressure with 15 MPa is pressed into thin slice again, promptly can be used as lithium ion battery negative.
The test of electrode electro Chemical performance adopts CR2025 type button simulated battery to test.Foam CuO/Cu with above-mentioned surperficial uncoated conductive agent that makes and binding agent
2The foam CuO/Cu of O/Cu material and surface-coated conductive agent and binding agent
2The O/Cu material is cut into the disk of required size, with lithium sheet (Chun Du>99.9%) conduct is to electrode, and PE monofilm (ENTEK) is a 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 accomplishes, and is full of high-purity argon gas, H in the glove box
2O, O
2Content utilizes sealing machine to seal in glove box all less than 0.1 ppm at last.
(specification 5V 2mA) carries out the constant current charge-discharge test to the simulated battery that is assembled to adopt the Land battery test system.Charging and discharging currents is 67 mA/g, and voltage range is 0.02-2.5 V.The present invention's used active material quality when calculating charging and discharging capacity does not comprise foam CuO/Cu
2The quality of the contained body Cu that dams in the O/Cu material.Electrochemical property test shows that constantly decline is different at the cyclic process capacity with general oxide cathode material, and this surfaces coated is covered with the foam CuO/Cu of conductive agent and binding agent
2The O/Cu material is as lithium ion battery negative, and after the loss of capacity only appears at 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 surface-coated of present embodiment preparation and the foam CuO/Cu of uncoated conductive agent and binding agent
2Fig. 1 is seen 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 from Fig. 1 it is thus clear that than the surface
2The O/Cu electrode, the capacity of negative plates of coated with conductive agent and binding agent is improved significantly.
Embodiment 2
To be 50% foam copper with porosity carry out surface acid with the nitric acid of 0.05 mol/L to it handles, and water cleans the back oven dry again; Foam copper after the oven dry is carried out compaction treatment under 20 MPa pressure; Foam copper after the compaction treatment is placed heat-treatment furnace, be 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
2The O/CuO oxide obtains foam Cu
2The O/CuO/Cu material is cooled to room temperature then.
Conductive agent acetylene black, binding agent PVDF (polyvinylidene fluoride), solvent NMP (N-methyl pyrrolidone) are mixed with slurry with the mass ratio of 1:0.5:10, stir.With the slurry brushing at the above-mentioned foam Cu that makes
2The O/CuO/Cu material surface, oven dry then, the pressure with 20 MPa is pressed into thin slice again, promptly gets lithium ion battery negative.
The foam Cu that makes
2The sem photograph (SEM) of the surface of O/CuO/Cu material under different amplification seen Fig. 2, and wherein figure (a) has shown this foam Cu
2The three-dimensional structure pattern of O/CuO/Cu material, it is thus clear that this material surface does not have and peels off and crackle, copper oxide combines well with the copper substrate among the figure; Figure (b) shows the pattern of the Cu oxide of this material surface, and visible this material list face length has the graininess Cu oxide among the figure.
Adopt to prepare CR2025 type button simulated battery with embodiment 1 identical method, and the simulated battery that is assembled is carried out the constant current charge-discharge test, its cycle performance is seen Fig. 3.The negative pole of present embodiment preparation is after circulation first, and capacity promptly no longer descends, and shows higher capacity and good cyclical stability.Reversible capacity is 352 mAh/g first, and specific discharge capacity constantly rises in cyclic process, through reaching 442 mAh/g after 40 circulations, apparently higher than the theoretical capacity of commercial carbon negative pole.Because the capacity of negative pole constantly increases in cyclic process, electrode life is long, and capacity is high.
Embodiment 3
To be 85% foam copper with porosity carry out surface acid with the acetic acid of 2 mol/L to it handles, and water cleans the back oven dry again; Foam copper after the oven dry is carried out compaction treatment under 2 MPa pressure; Foam copper after the compaction treatment is placed heat-treatment furnace, be 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
2The O/Cu material is cooled to room temperature then.
With mass ratio is that the conductive agent acetylene black of 7:3 and mixture, binding agent PVDF (polyvinylidene fluoride), the solvent NMP (N-methyl pyrrolidone) of carbon black are mixed with slurry with 1:2:100, stirs.With the above-mentioned foam Cu that makes
2The O/Cu material immerses in the slurry, subsequently its proposition is drained unnecessary slurry, oven dry, and the pressure with 18 MPa is pressed into thin slice again, promptly gets lithium ion battery negative.
Adopt to prepare CR2025 type button simulated battery with embodiment 1 identical method, and the simulated battery that is assembled is carried out the constant current charge-discharge test, the negative pole of present embodiment preparation is after discharge first, and capacity promptly no longer descends, and shows good cyclical stability.The long service life of electrode, capacity is high.Reversible capacity is 220 mAh/g first, and capacity remains 310 mAh/g after 60 circulations, and its cycle performance is seen Fig. 4.
Embodiment 4
To be 60% foam copper with porosity carry out surface acid with the phosphoric acid of 1 mol/L to it handles, and water cleans the back oven dry again; Foam copper after the oven dry is carried out compaction treatment under 10 MPa pressure; Foam copper after the compaction treatment is placed heat-treatment furnace, be warming up to 600 ° of C, in air atmosphere, carry out thermal oxidative reaction; Be incubated 5 hours; At foam copper surface in situ growth thickness is the stratiform CuO of 2 μ m, obtains foam CuO/Cu material, is cooled to room temperature then.
With mass ratio is conductive agent acetylene black and the Graphene mixture of 8:2, binding agent CMC (sodium carboxymethylcellulose),, solvent NMP (N-methyl pyrrolidone) is mixed with slurry with the mass ratio of 1:1:40, stir.At the above-mentioned foam CuO/Cu material surface that makes, after the oven dry, the pressure with 10 MPa is pressed into thin slice again, promptly gets lithium ion cell electrode with the slurry brushing.
Adopt and prepare CR2025 type button simulated battery with embodiment 1 identical method; And the simulated battery that is assembled is carried out constant current charge-discharge test; The good cyclical stability of negative pole performance of present embodiment preparation; Reversible capacity is 180 mAh/g first, and capacity remains 260 mAh/g after 60 circulations.Capacity constantly increases in cyclic process, the long service life of negative pole.
Embodiment 5
To be 60% foam copper with porosity carry out surface acid with the sulfuric acid of 0.05 mol/L to it handles, and water cleans the back oven dry again; Foam copper after the oven dry is carried out compaction treatment under 10MPa pressure; Foam copper after the compaction treatment is placed heat-treatment furnace, be 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 be a small amount of Cu that advocates peace with CuO
2The stratiform CuO/Cu of O
2The O compound obtains foam CuO/Cu
2The O/Cu material is cooled to room temperature then.The X-ray diffracting spectrum of this material is seen Fig. 5, and the Cu oxide layer on visible foam copper surface includes CuO and Cu among the figure
2O.
Conductive agent Graphene, binding agent CMC (sodium carboxymethylcellulose), solvent NMP (N-methyl pyrrolidone) are mixed with slurry with the mass ratio of 1:1:80, stir.The above-mentioned foam CuO/Cu that makes is immersed in the slurry, subsequently its proposition is drained unnecessary slurry, oven dry, the pressure with 20 MPa is pressed into thin slice again, promptly gets lithium ion cell electrode.
Adopt to prepare CR2025 type button simulated battery with embodiment 1 identical method, and the simulated battery that is assembled is carried out the constant current charge-discharge test, the negative pole of present embodiment preparation capacity after discharge does not first promptly descend, and shows good cyclical stability.Capacity of negative plates constantly increases in cyclic process, the long service life of negative pole, and capacity is high.Reversible capacity is 250 mAh/g first, and capacity remains 330 mAh/g after 60 circulations, and its cycle performance is seen Fig. 6.
Claims (8)
1. foam copper oxide/copper lithium ion battery negative; 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; Be covered with conductive agent and binding agent in its surfaces coated again, the thickness of described layered copper oxide is 200nm ~ 2 μ m, and described foam copper oxide/copper negative pole has three-dimensional structure.
2. foam copper oxide according to claim 1/copper lithium ion battery negative is characterized in that: described Cu oxide is CuO (cupric oxide), Cu
2O (cuprous oxide) or both mixtures.
3. the method for preparing foam copper oxide as claimed in claim 1/copper lithium ion battery negative; It is characterized in that: at collector foam copper surface in situ growth layered copper oxide, contain the coating of carbon back conductive agent and binding agent in foam copper oxide/copper surface-coated then through thermal oxidation method.
4. the method for preparing foam copper oxide/copper lithium ion battery negative according to claim 3 comprises the steps:
(1) foam copper is carried out surface acid-washing and handle, water cleans and oven dry again;
(2) foam copper after will drying carries out compaction treatment under 2 ~ 20 MPa pressure;
(3) foam copper after compaction treatment is placed 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 cooled to room temperature then;
(4) will contain carbon back conductive agent, binding agent and solvent and be mixed with slurry, at above-mentioned foam copper oxide/copper product surface-coated slurry, then with its oven dry;
(5) surface after will drying scribble carbon containing base conductive agent and binding agent foam copper oxide/copper product at 10 ~ 20MPa pressure pressed flakiness, promptly get foam copper oxide/copper lithium ion battery negative.
5. the method for preparing foam copper oxide/copper lithium ion battery negative 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 are 200 nm ~ 2 μ m.
6. the method for preparing foam copper oxide/copper lithium ion battery negative according to claim 4 is characterized in that: the acid described in the step (1) is hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid or nitric acid, and its molar concentration is 0.05 ~ 2 mol/L.
7. the method for preparing foam copper oxide/copper lithium ion battery negative according to claim 4; It is characterized in that: contain a kind of or any mixture that the carbon back conductive agent is acetylene black, carbon black or Graphene described in the step (4); Described binding agent is polyvinylidene fluoride or sodium carboxymethylcellulose, and described solvent is the N-methyl pyrrolidone.
8. the method for preparing foam copper oxide/copper lithium ion battery negative according to claim 4 is characterized in that: the mass ratio that contains carbon back conductive agent, binding agent and solvent described in the step (4) is 1:0.5 ~ 2:10 ~ 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110391054.1A CN102394305B (en) | 2011-11-30 | 2011-11-30 | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110391054.1A CN102394305B (en) | 2011-11-30 | 2011-11-30 | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102394305A true CN102394305A (en) | 2012-03-28 |
| CN102394305B CN102394305B (en) | 2014-07-30 |
Family
ID=45861561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110391054.1A Expired - Fee Related CN102394305B (en) | 2011-11-30 | 2011-11-30 | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102394305B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637860A (en) * | 2012-04-25 | 2012-08-15 | 浙江凯恩电池有限公司 | CuO/Cu composite anode material used for lithium ion battery as well as preparation method and application thereof |
| CN103611535A (en) * | 2013-11-19 | 2014-03-05 | 上海大学 | Preparation method of copper-foam-based hierarchical composite oxide monolithic denitrification catalyst |
| CN104868098A (en) * | 2015-05-15 | 2015-08-26 | 三峡大学 | Negative electrode of carbon-composite Cu3P-Cu lithium-ion battery and preparation method of negative electrode |
| CN106207090A (en) * | 2016-07-29 | 2016-12-07 | 四川大学 | Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type lithium ion battery negative and one one-step preparation method |
| CN106571473A (en) * | 2016-10-26 | 2017-04-19 | 济南大学 | Preparation method of Cu/Cu2O/CuO three-dimensional composite material having hierarchical pore structure |
| CN107302092A (en) * | 2016-04-14 | 2017-10-27 | 丰田自动车株式会社 | Collector, battery and their manufacture method |
| CN107572577A (en) * | 2017-10-29 | 2018-01-12 | 王兴利 | A kind of copper oxide nanocrystal material available for degrading nitrobenzene and preparation method thereof |
| CN107601550A (en) * | 2017-10-25 | 2018-01-19 | 王兴利 | It is a kind of to can be used for reducing agaric shape copper oxide nano material of m-chlorotoluene production waste water COD and preparation method thereof |
| CN107768600A (en) * | 2017-09-26 | 2018-03-06 | 华南师范大学 | A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof |
| CN108598489A (en) * | 2018-01-29 | 2018-09-28 | 东莞市航盛新能源材料有限公司 | A kind of 3D complex coppers and preparation method thereof and a kind of collector and its application |
| CN109713279A (en) * | 2018-12-29 | 2019-05-03 | 江西正拓新能源科技股份有限公司 | The preparation method of the lithium ion battery negative material of foam copper oxide-base |
| CN109888167A (en) * | 2019-02-21 | 2019-06-14 | 三峡大学 | A kind of copper-based self-supporting CuO-Cu2The preparation method of O composite array sodium ion negative electrode material |
| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN112892535A (en) * | 2021-03-05 | 2021-06-04 | 内蒙古大学 | Cu for VOC purificationxPreparation of O/Cu trans-photocatalytic material |
| CN113667909A (en) * | 2021-08-19 | 2021-11-19 | 西北工业大学 | Method for preparing lithium-philic copper current collector material by using T2 red copper |
| CN114335441A (en) * | 2021-12-30 | 2022-04-12 | 哈尔滨工业大学 | Crystalline Cu2Preparation method of O composite metal lithium cathode |
| CN114975880A (en) * | 2022-05-31 | 2022-08-30 | 华南师范大学 | Method for constructing composite lithium metal negative electrode by modifying surface of foamy copper and application of method |
| CN116190559A (en) * | 2023-05-04 | 2023-05-30 | 北京金羽新材科技有限公司 | Lithium-free negative electrode plate and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013470A (en) * | 2010-11-17 | 2011-04-13 | 哈尔滨工业大学 | Foam metal matrix oxide electrode used in lithium-ion battery cathode and preparation method thereof |
-
2011
- 2011-11-30 CN CN201110391054.1A patent/CN102394305B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013470A (en) * | 2010-11-17 | 2011-04-13 | 哈尔滨工业大学 | Foam metal matrix oxide electrode used in lithium-ion battery cathode and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 《Journal of Nanomaterials》 20081231 Benjamin.J.Hansen et al Direct Oxidation Growth of CuO Nanowires from Copper-Containing Substrates 3－8 第2008卷, * |
| 《无机化学学报》 20100531 王崇等 新型锂离子电池三维结构泡沫NiO电极的制备及电化学性能 摘要，1实验部分的1.1三维结构泡沫氧化镍电极的制备，2结果与讨论部分第1-2段，3结论部分 3－8 第26卷, 第5期 * |
| BENJAMIN.J.HANSEN ET AL: "Direct Oxidation Growth of CuO Nanowires from Copper-Containing Substrates", 《JOURNAL OF NANOMATERIALS》, vol. 2008, 31 December 2008 (2008-12-31) * |
| VENKATACHALAM.ETAL: "In-situ formation of sandwiched structures of nanotube/CuxOy/Cu composites for lithium battery applications", 《AMERICAN CHEMICAL SOCIETY NANO》, vol. 3, no. 8, 31 December 2009 (2009-12-31), pages 2177 - 2184 * |
| 王崇等: "新型锂离子电池三维结构泡沫NiO电极的制备及电化学性能", 《无机化学学报》, vol. 26, no. 5, 31 May 2010 (2010-05-31) * |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637860B (en) * | 2012-04-25 | 2014-06-04 | 浙江凯恩电池有限公司 | CuO/Cu composite anode material used for lithium ion battery as well as preparation method and application thereof |
| CN102637860A (en) * | 2012-04-25 | 2012-08-15 | 浙江凯恩电池有限公司 | CuO/Cu composite anode material used for lithium ion battery as well as preparation method and application thereof |
| CN103611535A (en) * | 2013-11-19 | 2014-03-05 | 上海大学 | Preparation method of copper-foam-based hierarchical composite oxide monolithic denitrification catalyst |
| CN103611535B (en) * | 2013-11-19 | 2016-01-13 | 上海大学 | The preparation method of foam copper base hierarchy composite oxide monolithic denitrification catalyst |
| CN104868098B (en) * | 2015-05-15 | 2018-03-27 | 三峡大学 | A kind of carbon composite Cu3P Cu negative electrode of lithium ion battery and preparation method thereof |
| CN104868098A (en) * | 2015-05-15 | 2015-08-26 | 三峡大学 | Negative electrode of carbon-composite Cu3P-Cu lithium-ion battery and preparation method of negative electrode |
| CN107302092B (en) * | 2016-04-14 | 2020-04-24 | 丰田自动车株式会社 | Current collector, battery, and methods for producing them |
| CN107302092A (en) * | 2016-04-14 | 2017-10-27 | 丰田自动车株式会社 | Collector, battery and their manufacture method |
| US11258069B2 (en) | 2016-04-14 | 2022-02-22 | Toyota Jidosha Kabushiki Kaisha | Current collector, battery and methods for producing the same |
| CN106207090B (en) * | 2016-07-29 | 2019-02-15 | 四川大学 | Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery and one one-step preparation method |
| CN106207090A (en) * | 2016-07-29 | 2016-12-07 | 四川大学 | Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type lithium ion battery negative and one one-step preparation method |
| CN106571473A (en) * | 2016-10-26 | 2017-04-19 | 济南大学 | Preparation method of Cu/Cu2O/CuO three-dimensional composite material having hierarchical pore structure |
| CN107768600A (en) * | 2017-09-26 | 2018-03-06 | 华南师范大学 | A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof |
| CN107768600B (en) * | 2017-09-26 | 2019-10-11 | 华南师范大学 | A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof |
| CN107601550B (en) * | 2017-10-25 | 2019-07-02 | 王兴利 | A kind of agaric shape copper oxide nano material and preparation method thereof can be used for reducing m-chlorotoluene production waste water COD |
| CN107601550A (en) * | 2017-10-25 | 2018-01-19 | 王兴利 | It is a kind of to can be used for reducing agaric shape copper oxide nano material of m-chlorotoluene production waste water COD and preparation method thereof |
| CN107572577A (en) * | 2017-10-29 | 2018-01-12 | 王兴利 | A kind of copper oxide nanocrystal material available for degrading nitrobenzene and preparation method thereof |
| CN108598489A (en) * | 2018-01-29 | 2018-09-28 | 东莞市航盛新能源材料有限公司 | A kind of 3D complex coppers and preparation method thereof and a kind of collector and its application |
| CN109713279A (en) * | 2018-12-29 | 2019-05-03 | 江西正拓新能源科技股份有限公司 | The preparation method of the lithium ion battery negative material of foam copper oxide-base |
| CN109888167A (en) * | 2019-02-21 | 2019-06-14 | 三峡大学 | A kind of copper-based self-supporting CuO-Cu2The preparation method of O composite array sodium ion negative electrode material |
| CN112349875A (en) * | 2020-10-23 | 2021-02-09 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN112349875B (en) * | 2020-10-23 | 2021-08-10 | 四川大学 | Lithium ion battery copper-copper oxide integrated cathode based on hollow tubular three-dimensional nano porous structure and preparation method |
| CN112892535A (en) * | 2021-03-05 | 2021-06-04 | 内蒙古大学 | Cu for VOC purificationxPreparation of O/Cu trans-photocatalytic material |
| CN113667909A (en) * | 2021-08-19 | 2021-11-19 | 西北工业大学 | Method for preparing lithium-philic copper current collector material by using T2 red copper |
| CN114335441A (en) * | 2021-12-30 | 2022-04-12 | 哈尔滨工业大学 | Crystalline Cu2Preparation method of O composite metal lithium cathode |
| CN114975880A (en) * | 2022-05-31 | 2022-08-30 | 华南师范大学 | Method for constructing composite lithium metal negative electrode by modifying surface of foamy copper and application of method |
| CN114975880B (en) * | 2022-05-31 | 2024-01-12 | 华南师范大学 | Method for constructing composite lithium metal negative electrode by modifying surface of foam copper and application of method |
| CN116190559A (en) * | 2023-05-04 | 2023-05-30 | 北京金羽新材科技有限公司 | Lithium-free negative electrode plate and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102394305B (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102394305B (en) | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof | |
| CN109004199B (en) | Preparation method of biomass hard carbon material for negative electrode of sodium-ion battery | |
| CN108376783B (en) | Lithium anode surface protective coating and preparation method thereof | |
| CN106159318A (en) | Novel slice type solid-state serondary lithium battery that garnet-type solid electrolyte supports and preparation method thereof | |
| CN110112367B (en) | Three-dimensional composite metal lithium cathode, preparation method thereof, lithium metal battery and lithium sulfur battery | |
| CN108417813A (en) | A kind of preparation method of lithium ion battery negative material | |
| CN102339982A (en) | Anode of lithium ion battery, preparation method and battery using anode | |
| CN108923037B (en) | Silicon-rich SiOx-C material and preparation method and application thereof | |
| CN102427129A (en) | Lithium ion battery composite negative electrode material, its preparation method, negative electrode with application of material thereof and lithium ion battery | |
| CN105609761B (en) | A kind of application of CuCl/Cu composite materials | |
| CN109524649B (en) | Sodium-ion battery positive electrode material with coating structure and preparation method and application thereof | |
| CN110957477B (en) | Porous ceramic composite lithium metal cathode and preparation method thereof | |
| CN111769288B (en) | Method for in-situ lithium supplement of lithium ion battery anode material | |
| CN105742695B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN110890530B (en) | Lithium metal secondary battery based on porous ceramic composite lithium metal cathode and preparation method thereof | |
| CN110148730A (en) | A kind of Gao Shouxiao long-life silicon based anode material and its preparation method and application | |
| CN103000874A (en) | Preparation method of carbon-coated ternary positive electrode material | |
| CN104022269B (en) | A kind of native graphite and MnO composite high-performance electrode material and preparation method thereof | |
| CN104966814A (en) | High-security metallic lithium cathode and preparation method thereof | |
| CN110627031A (en) | Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material | |
| CN102332582B (en) | Preparation method for novel lithium vanadium phosphate/bamboo charcoal composite cathode material | |
| CN112103499B (en) | Graphene-based negative electrode material and preparation method thereof | |
| CN103378355A (en) | Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance | |
| CN105226251A (en) | A kind of pure carbon compound cathode materials and preparation method thereof | |
| CN113451547B (en) | Composite metal lithium cathode and lithium ion battery comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140730 Termination date: 20211130 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |