CN102339982A - Anode of lithium ion battery, preparation method and battery using anode - Google Patents
Anode of lithium ion battery, preparation method and battery using anode Download PDFInfo
- Publication number
- CN102339982A CN102339982A CN2011103159317A CN201110315931A CN102339982A CN 102339982 A CN102339982 A CN 102339982A CN 2011103159317 A CN2011103159317 A CN 2011103159317A CN 201110315931 A CN201110315931 A CN 201110315931A CN 102339982 A CN102339982 A CN 102339982A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- paper tinsel
- ion battery
- collector
- cuo
- 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.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 relates to an anode of a lithium ion battery, a preparation method for the anode and the battery using the anode. A cupric oxide (CuO) thin film is grown in situ on the surface of a current collector Cu foil by a thermal oxidation method for heating in an oxidizing atmosphere, and the current collector Cu foil and the CuO thin film grown in situ on the surface of the current collector Cu foil can be directly used as the anode of the lithium ion battery. A fussy and complex coating process required by the conventional preparation of the anode of the lithium ion battery is not required. The anode has high electrode capacity and high cyclical stability, and solves the problem that the high capacity and high cyclical stability of a commercial lithium ion anode material cannot be achieved at the same time. The preparation method provided by the invention is simple and easy to control, low in environmental requirements, high in electrode specific capacity and cycle performance and applied to the industrial application of the lithium ion battery.
Description
Technical field
The present invention relates to a kind of lithium ion battery, relate in particular to a kind of negative pole and preparation method thereof and the battery that uses this negative pole of lithium ion battery.
Background technology
Lithium ion battery is the green energy resource that grows up the nineties in 20th century; Compare with secondary cells such as traditional plumbic acid, NI-G, ni-mhs; Lithium ion battery enjoys favor with advantage such as its high reversible capacity, good cycle performance and high-energy-density, memory-less effect, is one of focus of countries in the world secondary energy sources research and development over surplus in the of nearly ten year.
Along with the requirement of lithium ion battery of new generation to electrode material improves gradually, traditional electrode material can not satisfy the demands, and therefore the research and development of various positive and negative pole materials launches.At present, commercial negative material with lithium ion battery mainly is a material with carbon element, and the theoretical capacity of carbon negative pole material is merely 372 mAh/g.Transition metal oxide is like CuO, NiO, CoO etc., because of its high theoretical capacity and fail safe preferably more and more receive publicity and favor.CuO is as a kind of typical three-dimensional transition metal oxide, band gap 1.2eV, and cheap, safety non-toxic has been widely used in magnetic-based storage media, solar energy converting, transducer and secondary cell etc.CuO is 670 mAh/g as the theoretical capacity of lithium ion battery negative material, is a kind of lithium ion battery negative material that has commercial application value.But then; The major defect that CuO exists as lithium ion battery negative material be since in the removal lithium embedded process change in volume of CuO cause the material efflorescence; Add the poorly conductive of CuO, electrically contact, reduced the specific capacity and the cycle performance of battery thereby the part active material is lost effectively.Therefore, need carry out modification, under the condition that keeps its high capacity characteristics, improve its cyclical stability the CuO material.Common modified method 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 and complicated both positive and negative polarity prepares process.In the production process of negative pole; At first to negative electrode active material, adhesive, conductive agent and solvent be processed slurry by certain proportioning, then slurry is coated in negative current collector Cu paper tinsel surface, so numerous and diverse technology through painting process; Make that the production cost of negative pole is higher, difficult quality control.In actual production, hope can be found a kind of technological process of simplifying, and reduces production costs, and has negative pole of high power capacity and good circulation stability and preparation method thereof concurrently.
Chinese patent CN102013470A discloses and has been used for foamed-metal based oxide electrode of lithium ion battery negative and preparation method thereof, and report foam Cu, Fe, Ni generate CuO, Fe through aqueous solution chlorination reaction original position down the auxiliary of surfactant
2O
3, NiO, thereby directly prepare the negative pole of lithium ion battery.Yet foam metal is higher relatively aspect the cost of raw material, and the aqueous solution chlorination method need add surfactant, and high to environmental requirement, process is wayward, is not suitable for the application that large-scale industrialization is produced.
Chinese patent CN101311363A discloses a kind of negative pole with bar-shaped CuO nanometer thin rete and preparation method thereof, promptly under 550 ℃ ~ 560 ℃ high temperature, obtains bar-shaped CuO nano-material in Cu paper tinsel original position.But because when preparation adopted high temperature, cause stress deformation easily, CuO is relatively poor with contacting of Cu matrix, is prone to come off, and causes the reduction of capacity of lithium ion battery, and the CuO rod exposes barrier film easily and cause battery short circuit, causes potential safety hazard.Therefore adopt the method for simply in oxidizing atmosphere, carrying out thermal oxidation to generate the CuO film at Cu paper tinsel collection liquid surface; Through to oxidizing temperature and isoparametric control of oxidization time and process optimization; Improve the chemical property of synthetic negative pole, be expected to become a kind of desirable method for preparing high-performance CuO negative pole.
Summary of the invention
First purpose of the present invention provides a kind of negative pole of lithium ion battery, has high power capacity, good cyclical stability, the simple advantage of preparation method.For this reason, the present invention adopts following technical scheme: it has the CuO film through thermal oxidation method in the growth of collector Cu paper tinsel surface in situ, and the CuO film of collector Cu paper tinsel and the growth of its surface in situ directly is used as the negative pole of lithium ion battery.
Further, described collector Cu paper tinsel thickness is 10 ~ 100 μ m.
Second purpose of the present invention provides a kind of lithium ion battery, and it is simple to have preparation technology, and capacity is high, the advantage of good cycling stability.For this reason, the present invention adopts following technical scheme: comprise above-mentioned negative pole, positive pole that can the removal lithium embedded ion, and electrolyte and barrier film between said negative pole and said positive pole.
The 3rd purpose of the present invention is the deficiency that overcomes prior art, provides a kind of at negative current collector Cu paper tinsel surface in situ growth CuO film, directly prepares the method for lithium ion battery negative.
Can directly prepare the negative pole of lithium ion battery according to this method, save operations such as joining the slurry pasting, simplify technological process, be fit to very much commercially producing of lithium ion battery.
The technical scheme that the present invention adopts is: through the thermal oxidation method that in oxidizing atmosphere, heats at collector Cu paper tinsel surface in situ growth CuO film; The CuO film of collector Cu paper tinsel and the growth of its surface in situ; Through simple shearing and assembling, promptly become the negative pole of lithium ion battery.
The method of wherein said collector Cu paper tinsel surface in situ growth CuO film comprises the steps:
(1) collector Cu paper tinsel is carried out surface acid-washing and handle, use washed with de-ionized water again, and the Cu paper tinsel that will clean is dry;
(2) dried Cu paper tinsel is placed heating furnace, be warming up to 200 ℃ ~ 500 ℃, carry out thermal oxidation, be incubated 0.5 ~ 20 hour, obtain the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
Collector Cu paper tinsel thickness the best wherein of the present invention is 10 ~ 100 μ m;
The atmosphere of above-mentioned thermal oxidation is air or oxygen.
When being oxidizing atmosphere, adopt non-hermetic type heating furnace with the air; When being oxidizing atmosphere with oxygen, adopt hermetic type atmosphere heating furnace, oxygen gas flow rate is the oxygen of 10 mL/min ~ 100 mL/min.
Beneficial effect of the present invention is following:
The CuO film of 1) growing at collector Cu paper tinsel surface in situ has according to the method for the invention guaranteed good electrical contact between CuO film and the Cu matrix, makes it have good dynamic performance, charge/discharge capacity and cyclical stability.
2) the present invention has kept the thinner particle size that low-temperature oxidation had through the control to oxidizing temperature, thereby has guaranteed the good dynamic performance of CuO film cathode, has improved its cyclical stability.
3) the present invention is through the control to oxidization time, the thickness and the particle size of the CuO film that the may command oxidation is obtained, thereby the CuO film cathode that can obtain to have high power capacity and good dynamics performance.
4) the CuO film cathode active material of the present invention's preparation is generated in-situ on Cu matrix, goes back reserve part Cu phase in the film, because Cu has high conductivity mutually, thereby has improved the conductivity of CuO active material, has improved the dynamic performance of electrode.
According to method of the present invention; The thermal oxidation method that in oxidizing atmosphere, heats directly prepares lithium ion battery negative at collector Cu paper tinsel surface in situ growth CuO film, and the particle size of CuO film and film thickness can effectively be controlled, and the conductivity of negative material is high; The negative pole of preparation has high charge/discharge capacity and good cyclical stability concurrently; And preparation technology is simple, is suitable for commercially producing, and has saved coating, has joined operations such as slurry, pasting; Need not to use auxiliary material such as binding agent and conductive agent, have bigger commercial application value.
Description of drawings
Fig. 1 a is the ESEM picture of the CuO film of embodiment 1 preparation;
Fig. 1 b is the ESEM picture of the CuO film of embodiment 2 preparations;
Fig. 1 c is the ESEM picture of the CuO film of embodiment 3 preparations;
Fig. 2 is the specific discharge capacity cyclic curve figure of CuO film cathode under 0.1C of embodiment 1 preparation;
Fig. 3 is the specific discharge capacity cyclic curve figure of CuO film cathode under 0.1C of embodiment 2 preparations;
Fig. 4 is the specific discharge capacity cyclic curve figure of CuO film cathode under 0.1C of embodiment 3 preparations;
Fig. 5 is the specific discharge capacity cyclic curve figure of CuO film cathode under 0.1C of embodiment 4 preparations;
Fig. 6 is the specific discharge capacity cyclic curve figure of CuO film cathode under 0.1C of embodiment 5 preparations.
The practical implementation method
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that, these embodiment only be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition that after the content of having read instruction of the present invention those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The preparation of CuO film: select for use the thick Cu paper tinsel of 20 μ m as collector Cu paper tinsel, this Cu paper tinsel is carried out surface acid-washing with the hydrochloric acid of 1.0 mol/L handle, use washed with de-ionized water again; The Cu paper tinsel that cleaned is placed airtight tube furnace; Drying at room temperature 1.5 h under argon shield, the temperature of airtight tube furnace is warming up to 300 ℃ with 10 ℃/min speed after aerating oxygen, flow velocity is 40 mL/min; Be incubated 2 h, obtain the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
The pattern of CuO film: the pattern of the CuO film that makes through sem observation, the ESEM picture is seen Fig. 1 a.Visible by figure, the CuO particle has certain gap, and vertical Cu paper tinsel surface direction length has tiny corynebacterium structure.
The preparation of lithium ion battery negative: the collector Cu paper tinsel that superficial growth is had the CuO film is at 120 ℃ of vacuumize 2h, rolling formation, and cut-parts make 53 millimeters * 30 millimeters negative pole.
The preparation of lithium ion cell positive: 100 gram polyvinylidene fluoride (PVDF) are dissolved in N-methyl pyrrolidone (NMP) solvent make binder solution; Then 800 gram LiFePO4s and 100 are restrained the acetylene black powder serve as conductive agent and join in the above-mentioned solution, be stirred well to mix and make anode sizing agent; Using tensile pulp machine that anode sizing agent is coated in thickness equably is 1.5 millimeters aluminium foil two sides.Through 120 ℃ of vacuumize 2h, rolling formation, cut-parts make 53 millimeters * 30 millimeters positive pole.
The preparation of lithium ion battery: the above-mentioned positive pole that makes, barrier film, negative pole and barrier film lamination successively included in after good in 55 millimeters * 34 millimeters * 6 millimeters the square aluminum hull; With volume ratio is the lithium hexafluoro phosphate (LiPF of 1:1:1
6) the electrolyte of ethylene carbonate, Methylethyl carbonic ester and diethyl carbonate inject above-mentioned battery; The sealed cell aluminum hull can obtain lithium ion battery of the present invention.
The chemical property of CuO film cathode: being assembled in of Experimental cell is full of high-purity argon gas, H
2O, O
2Content is all less than carrying out in the glove box of 0.1 ppm.Adopting CR2025 type button cell is simulated battery, and with the superficial growth that makes the collector Cu paper tinsel of CuO film being arranged is negative pole, lithium sheet (Chun Du>99.9%) conduct is to electrode, and PE monofilm (ENTEK) is a barrier film, and electrolyte is 1 mol/L LiPF
6The mixed solution of ethylene carbonate (EC)/dimethyl carbonate (DMC).Simulated battery is carried out 100 times charge-discharge performance and cycle performance test, and the result shows good specific capacity and stable circulation performance, is 485.4 mAh/g after 100 circulations of the specific discharge capacity under the 0.1C, and the specific discharge capacity cyclic curve is as shown in Figure 2.
Embodiment 2
The preparation of CuO film: select for use the thick Cu paper tinsel of 20 μ m as collector Cu paper tinsel, this Cu paper tinsel is carried out surface acid-washing with the hydrochloric acid of 0.5 mol/L handle, use washed with de-ionized water again; Cu paper tinsel air dry in air of cleaning is placed in the airtight tube furnace; Aerating oxygen after the temperature of airtight tube furnace is warming up to 250 ℃ with 5 ℃/min speed; Flow velocity is 50 mL/min, is incubated 10 hours, obtains the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
The pattern of CuO film: the pattern of the CuO film that makes through sem observation, the ESEM picture is seen Fig. 1 b.Visible by figure, particle size is less and even, and intergranular dispersiveness is better, and vertical Cu paper tinsel surface direction length has linear structure.
According to preparing negative pole and the lithium ion battery that comprises this negative pole with embodiment 1 identical method.
The chemical property of CuO film cathode: the collector Cu paper tinsel that the superficial growth that present embodiment is made has the CuO film is as negative pole; According to preparing simulated battery with embodiment 1 identical method; Charge-discharge performance and cycle performance that this battery is carried out 100 times are tested; The result shows good specific capacity and stable circulation performance, is 536.8 mAh/g after 100 circulations of the specific discharge capacity under the 0.1C, and the specific discharge capacity cyclic curve is as shown in Figure 3.
Embodiment 3
The preparation of CuO film: select for use the thick Cu paper tinsel of 30 μ m as collector Cu paper tinsel, this Cu paper tinsel is carried out surface acid-washing with the acetic acid of 1.0 mol/L handle, use washed with de-ionized water again; The Cu paper tinsel that cleaned is placed airtight tube furnace, drying at room temperature 2 h under nitrogen protection; Aerating oxygen after the temperature of airtight tube furnace is warming up to 350 ℃ with 15 ℃/min speed, flow velocity is 100 mL/min, is incubated 0.5 h, obtains the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
The pattern of CuO film: the pattern of the CuO film that makes through sem observation, the ESEM picture is seen Fig. 1 c.Visible by figure, the particle size size is more even, and each other dispersed fine has very big space, and vertically Cu paper tinsel surface direction length has thin club shaped structure.
According to preparing negative pole and the lithium ion battery that comprises this negative pole with embodiment 1 identical method.
The chemical property of CuO film cathode: the collector Cu paper tinsel that the superficial growth that present embodiment is made has the CuO film is as negative pole; According to preparing simulated battery with embodiment 1 identical method; Charge-discharge performance and cycle performance that this battery is carried out 100 times are tested; The result shows good specific capacity and stable circulation performance, is 454.7 mAh/g after 100 circulations of the specific discharge capacity under the 0.1C, and the specific discharge capacity cyclic curve is as shown in Figure 4.
Embodiment 4
The preparation of CuO film: select for use the thick Cu paper tinsel of 20 μ m as collector Cu paper tinsel, this Cu paper tinsel is carried out surface acid-washing with the hydrochloric acid of 1.0 mol/L handle, use washed with de-ionized water again; The Cu paper tinsel that cleaned drying at room temperature under the dynamic vacuum environment is placed in the common box type furnace, be warming up to 250 ℃ with 10 ℃/min speed after, insulation 4 h in the atmosphere obtain the CuO film on collector Cu paper tinsel surface after reducing to room temperature in air.
According to preparing negative pole and the lithium ion battery that comprises this negative pole with embodiment 1 identical method.
The chemical property of CuO film cathode: the collector Cu paper tinsel that the superficial growth that present embodiment is made has the CuO film is as negative pole; According to preparing simulated battery with embodiment 1 identical method; Charge-discharge performance and cycle performance that this battery is carried out 100 times are tested; The result shows good specific capacity and stable circulation performance, is 521.4 mAh/g after 100 circulations of the specific discharge capacity under the 0.1C, and the specific discharge capacity cyclic curve is as shown in Figure 5.
Embodiment 5
The preparation of CuO film: select for use the thick Cu paper tinsel of 10 μ m as collector Cu paper tinsel, this Cu paper tinsel is carried out surface acid-washing with the hydrochloric acid of 1.0 mol/L handle, use washed with de-ionized water again; The Cu paper tinsel that cleaned is placed airtight tube furnace, drying at room temperature 2 h under nitrogen protection; Aerating oxygen after the temperature of airtight tube furnace is warming up to 250 ℃ with 5 ℃/min speed, flow velocity is 50 mL/min, is incubated 10 h, obtains the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
According to preparing negative pole and the lithium ion battery that comprises this negative pole with embodiment 1 identical method.
The chemical property of CuO film cathode: the collector Cu paper tinsel that the superficial growth that present embodiment is made has the CuO film is as negative pole; According to preparing simulated battery with embodiment 1 identical method; Charge-discharge performance and cycle performance that this battery is carried out 100 times are tested; The result shows good specific capacity and stable circulation performance, is 541.6 mAh/g after 100 circulations of the specific discharge capacity under the 0.1C, and the specific discharge capacity cyclic curve is as shown in Figure 6.
Embodiment 6
The preparation of CuO film: select the thick refining Cu paper tinsel of 50 μ m for use, collector Cu paper tinsel is carried out surface acid-washing with the nitric acid of 0.02 mol/L handle, use washed with de-ionized water again; The Cu paper tinsel that cleaned drying under air is placed in the common box type furnace, the temperature of box type furnace is warming up to 200 ℃ with 5 ℃/min speed after, insulation 15 h in air atmosphere obtain the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
According to preparing negative pole and the lithium ion battery that comprises this negative pole with embodiment 1 identical method.
Embodiment 7
The preparation of CuO film: select the thick refining Cu paper tinsel of 100 μ m for use, collector Cu paper tinsel is carried out surface acid-washing with the phosphoric acid of 0.05 mol/L handle, use washed with de-ionized water again; Cu paper tinsel air dry in air of cleaning is placed in the common box type furnace, and heating furnace to 500 is incubated 20h ℃ under air conditions, obtains the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
According to preparing negative pole and the lithium ion battery that comprises this negative pole with embodiment 1 identical method.
Claims (8)
1. a lithium ion battery negative is characterized in that in the growth of collector Cu paper tinsel surface in situ the CuO film being arranged through thermal oxidation method, and the CuO film of collector Cu paper tinsel and the growth of its surface in situ directly is used as the negative pole of lithium ion battery.
2. lithium ion battery negative according to claim 1, the thickness that it is characterized in that the collector Cu paper tinsel of described superficial growth CuO is 10 ~ 100 μ m.
3. a lithium ion battery is characterized in that comprising negative pole according to claim 1 and 2, positive pole that can the removal lithium embedded ion, and electrolyte and barrier film between said negative pole and said positive pole.
4. the method for preparing the described lithium ion battery negative of claim 1; It is characterized in that it is at collector Cu paper tinsel surface in situ growth CuO film;, comprise the steps: directly as the negative pole of lithium ion battery by the CuO film of collector Cu paper tinsel and its surface in situ growth at collector Cu paper tinsel surface in situ growth CuO film
(1) collector Cu paper tinsel is carried out surface acid-washing and handle, use washed with de-ionized water again, and the Cu paper tinsel that will clean is dry;
(2) dried Cu paper tinsel is placed heating furnace, be warming up to 200 ℃ ~ 500 ℃, carry out thermal oxidation, be incubated 0.5 ~ 20 hour, obtain the CuO film on collector Cu paper tinsel surface after reducing to room temperature.
5. the preparation method of lithium ion battery negative according to claim 4 is characterized in that described collector Cu paper tinsel thickness is 10 ~ 100 μ m.
6. the preparation method of lithium ion battery negative according to claim 4 is characterized in that described acid is hydrochloric acid, acetic acid, phosphoric acid and nitric acid.
7. the preparation method of lithium ion battery negative according to claim 4 is characterized in that the thermal oxidation in the described step (2) is meant the heated oxide in oxidizing atmosphere.
8. the preparation method of lithium ion battery negative according to claim 7 is characterized in that described oxidizing atmosphere is meant air or oxygen.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710021157.6A CN106654170A (en) | 2011-10-18 | 2011-10-18 | High-performance negative electrode directly serving as lithium ion battery and battery using the negative electrode |
| CN2011103159317A CN102339982A (en) | 2011-10-18 | 2011-10-18 | Anode of lithium ion battery, preparation method and battery using anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103159317A CN102339982A (en) | 2011-10-18 | 2011-10-18 | Anode of lithium ion battery, preparation method and battery using anode |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710021157.6A Division CN106654170A (en) | 2011-10-18 | 2011-10-18 | High-performance negative electrode directly serving as lithium ion battery and battery using the negative electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102339982A true CN102339982A (en) | 2012-02-01 |
Family
ID=45515576
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103159317A Pending CN102339982A (en) | 2011-10-18 | 2011-10-18 | Anode of lithium ion battery, preparation method and battery using anode |
| CN201710021157.6A Pending CN106654170A (en) | 2011-10-18 | 2011-10-18 | High-performance negative electrode directly serving as lithium ion battery and battery using the negative electrode |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710021157.6A Pending CN106654170A (en) | 2011-10-18 | 2011-10-18 | High-performance negative electrode directly serving as lithium ion battery and battery using the negative electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN102339982A (en) |
Cited By (12)
| 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 |
| CN106328944A (en) * | 2016-11-14 | 2017-01-11 | 南开大学 | Method for in-situ preparation of cathode indium antimonide of binder-free lithium/sodium-ion battery on copper foil surface |
| 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 |
| CN109999805A (en) * | 2018-10-12 | 2019-07-12 | 中国科学院金属研究所 | One kind Cu-CuO containing three-dimensional porous structureXThe preparation method of heterojunction structure |
| CN110010971A (en) * | 2018-01-04 | 2019-07-12 | 通用汽车环球科技运作有限责任公司 | Method for manufacturing electrochemical cell |
| CN110137504A (en) * | 2019-06-17 | 2019-08-16 | 广东省半导体产业技术研究院 | A kind of secondary lithium battery cathode three-dimensional collector and preparation method thereof |
| CN110880595A (en) * | 2019-11-08 | 2020-03-13 | 重庆佳宝成能源科技有限公司 | Cu3Preparation method of P-CuO composite flexible lithium ion battery cathode material |
| CN113823767A (en) * | 2021-09-02 | 2021-12-21 | 南京航空航天大学 | Modified negative electrode for lithium metal battery and preparation method thereof |
| US11309539B2 (en) | 2018-01-04 | 2022-04-19 | GM Global Technology Operations LLC | Electrochemical cell and method of manufacturing |
| CN114388741A (en) * | 2022-02-25 | 2022-04-22 | 电子科技大学 | Sodium titanium phosphate electrode and preparation method thereof |
| US11502287B2 (en) | 2018-01-04 | 2022-11-15 | GM Global Technology Operations LLC | Method of manufacturing an electrochemical cell |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109713279B (en) * | 2018-12-29 | 2021-06-11 | 江西正拓新能源科技股份有限公司 | Preparation method of foamy copper oxide-based lithium ion battery negative electrode material |
| CN113390800B (en) * | 2020-03-13 | 2022-05-20 | 宁德新能源科技有限公司 | Method for detecting content of copper simple substance in lithium battery positive electrode material |
| CN111549321B (en) * | 2020-04-20 | 2022-04-29 | 湘潭大学 | Preparation method of lithium ion battery cathode material and related product thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100469685C (en) * | 2006-01-09 | 2009-03-18 | 合肥工业大学 | Production of oxide copper nanometer tube array |
| CN101429032B (en) * | 2007-11-06 | 2011-05-18 | 中国科学院化学研究所 | CuO-carbon nano-tube composite micro-nano-sphere, preparation and uses thereof |
-
2011
- 2011-10-18 CN CN2011103159317A patent/CN102339982A/en active Pending
- 2011-10-18 CN CN201710021157.6A patent/CN106654170A/en active Pending
Non-Patent Citations (5)
| Title |
|---|
| 《Journal of Nanomaterials》 20081231 Benjamin.J.Hansen et al Direct Oxidation Growth of CuO Nanowires from Copper-Containing Substrates 1-7 4-8 , * |
| BENJAMIN.J.HANSEN ET AL: "Direct Oxidation Growth of CuO Nanowires from Copper-Containing Substrates", 《JOURNAL OF NANOMATERIALS》 * |
| J.Y.XIANG ET AL: "A comparison of anodically grown CuO nanotube film and Cu2O film as anodes for lithium ion batteries", 《J SOLID STATE ELECTROCHEM》 * |
| QIMIN PAN ET AL: "Flower-like CuO film-electrode for lithium ion batteries and the effect of surface morphology on electrochemical performance", 《ELECTROCHIMICA ACTA》 * |
| 付丽君等: "锂离子电池纳米负极材料的研究和开发", 《复旦学报》 * |
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 |
| 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 |
| CN106328944A (en) * | 2016-11-14 | 2017-01-11 | 南开大学 | Method for in-situ preparation of cathode indium antimonide of binder-free lithium/sodium-ion battery on copper foil surface |
| CN106328944B (en) * | 2016-11-14 | 2019-06-21 | 南开大学 | Binder free lithium/two bronze medal of sodium-ion battery cathode antimonyization method is prepared in situ in a kind of copper foil surface |
| 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 |
| 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 |
| 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 |
| CN110010971A (en) * | 2018-01-04 | 2019-07-12 | 通用汽车环球科技运作有限责任公司 | Method for manufacturing electrochemical cell |
| US11309539B2 (en) | 2018-01-04 | 2022-04-19 | GM Global Technology Operations LLC | Electrochemical cell and method of manufacturing |
| CN110010971B (en) * | 2018-01-04 | 2022-09-20 | 通用汽车环球科技运作有限责任公司 | Method for manufacturing electrochemical cell |
| US11502287B2 (en) | 2018-01-04 | 2022-11-15 | GM Global Technology Operations LLC | Method of manufacturing an electrochemical cell |
| CN109999805A (en) * | 2018-10-12 | 2019-07-12 | 中国科学院金属研究所 | One kind Cu-CuO containing three-dimensional porous structureXThe preparation method of heterojunction structure |
| CN109999805B (en) * | 2018-10-12 | 2021-11-05 | 中国科学院金属研究所 | Cu-CuO containing three-dimensional porous structureXMethod for preparing heterostructure |
| CN110137504A (en) * | 2019-06-17 | 2019-08-16 | 广东省半导体产业技术研究院 | A kind of secondary lithium battery cathode three-dimensional collector and preparation method thereof |
| CN110880595A (en) * | 2019-11-08 | 2020-03-13 | 重庆佳宝成能源科技有限公司 | Cu3Preparation method of P-CuO composite flexible lithium ion battery cathode material |
| CN110880595B (en) * | 2019-11-08 | 2022-11-08 | 重庆市加鼎盛科技有限公司 | Cu 3 Preparation method of P-CuO composite flexible lithium ion battery cathode material |
| CN113823767A (en) * | 2021-09-02 | 2021-12-21 | 南京航空航天大学 | Modified negative electrode for lithium metal battery and preparation method thereof |
| CN114388741A (en) * | 2022-02-25 | 2022-04-22 | 电子科技大学 | Sodium titanium phosphate electrode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106654170A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102339982A (en) | Anode of lithium ion battery, preparation method and battery using anode | |
| CN102394305B (en) | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN108878849A (en) | The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium | |
| CN105355908B (en) | Composite cathode material for lithium ion cell and preparation method thereof, cathode and lithium ion battery using the material | |
| CN102231435B (en) | Method for preparing electrode material CuO (cupric oxide) film of lithium ion battery on copper substrate | |
| CN109148859B (en) | Preparation method of manganese oxide composite material coated by double carbon layers | |
| CN107732172B (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN109659540B (en) | Preparation method of porous carbon-coated antimony telluride nanosheet and application of porous carbon-coated antimony telluride nanosheet as negative electrode material of metal ion battery | |
| CN105047892A (en) | Porous silicon material, and preparation method and application thereof | |
| CN107275590A (en) | A kind of porous Si-C composite material and its preparation method and application | |
| CN114188502B (en) | Prussian white composite material and preparation method and application thereof | |
| CN109950523A (en) | Lithium ion battery negative material transition metal oxide/carbon preparation method | |
| CN103000879A (en) | Preparation method of spinel type lithium-nickel-manganese oxide with one-dimensional porous structure | |
| CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
| CN111261870B (en) | NASICON structure Na4CrMn(PO4)3Method for producing materials and use thereof | |
| CN105742619B (en) | A kind of unformed Mn oxide cladding ferriferous oxide lithium/anode material of lithium-ion battery and preparation method thereof | |
| CN116177556A (en) | Sodium-electricity positive electrode material, precursor thereof, preparation method and application | |
| CN109256547A (en) | A kind of preparation method of porous graphene-lithium iron phosphate positive material | |
| CN111354942B (en) | Micron-sized rod-shaped lithium manganate and preparation method and application thereof | |
| CN114142033A (en) | Modified graphite negative electrode material for lithium ion battery | |
| CN112614981A (en) | Two-dimensional sheet Fe for lithium ion battery3O4Preparation method of/C composite electrode material | |
| CN103474634B (en) | Two step synthesis nucleocapsid AgTiO 2the method of compound and the application as lithium ion battery negative | |
| CN114057230B (en) | Penicillium spore carbon/manganese dioxide composite material and preparation method and application thereof | |
| CN111092208B (en) | RGO modified Fe3O4-SnO2Preparation method and application of composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120201 |