CN101222047B - Cathode material of thin film lithium ion battery and method for producing the same - Google Patents
Cathode material of thin film lithium ion battery and method for producing the same Download PDFInfo
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- CN101222047B CN101222047B CN2008100591129A CN200810059112A CN101222047B CN 101222047 B CN101222047 B CN 101222047B CN 2008100591129 A CN2008100591129 A CN 2008100591129A CN 200810059112 A CN200810059112 A CN 200810059112A CN 101222047 B CN101222047 B CN 101222047B
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- 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 cathode material for a membrane lithium ion battery, which is a foaming nickel load NiO/Ag nano composite porous membrane, NiO with a mass percent of 75 percent to 95 percent, and nano metal Ag of 5 percent to 25 percent. The preparation method for the cathode material comprises the following steps: firstly, a foaming nickel substrate is laid into mixture of NiSO4 solution, K2S2O8 solution, strong aqua ammonia and water for sedimentation and then calcined in argon gas; secondly, the substrate after calcinations is laid into mixture of silver-ammonia solution and polyvinylpyrrolidone ethanol solution for continuous sedimentation. Compared with the prior NiO membrane cathode, a cathode of the foaming nickel load NiO/Ag nano composite porous membrane contains more active materials, and contact interface between an electrode and electrolytes is larger and lithium ion battery diffusion path is shorter. Moreover, the cathode still has high area specific capacity and superior cyclicity even under the condition of high rate.
Description
Technical field
The invention belongs to the negative material of film lithium ion battery, be specifically related to the preparation method of foamed nickel supported NiO/Ag porous film electrode.
Background technology
Film lithium ion battery is compared have the average voltage height (about 3.6V), capacity density height, memory-less effect, advantages such as non-environmental-pollution with traditional thin-film secondary battery.Traditional film lithium ion battery uses the collector of sheet metal as load thin film.The surface area of sheet metal is limited, causes the quality of the contained electroactive substance of film that deposits to be difficult to be implemented in industrial application very little.Though can be by increasing the quality that film thickness improve active material in the film, only depend on the increase of activity substance content of this acquisition limited.And because present most of film all is the compactness film, that improves that thickness must reduce film and substrate electrically contacts, reduces contact area between film and the electrolyte, and this chemical property that certainly will worsen film is battery capacity under high-multiplying power discharge and cycle performance especially.Transition metal oxide film is a kind of novel lithium ion battery negative material, but it is a semiconductor, can be by further improving the conductivity of film with the nano metal composite methods of good conductivity, thus the chemical property of film lithium ion battery electrode improved.
Summary of the invention
The objective of the invention is to provide negative material of a kind of film lithium ion battery that under the high power charging-discharging current density, has high area specific capacity and a good circulation performance and preparation method thereof.
The negative material of film lithium ion battery of the present invention is foamed nickel supported NiO/Ag nano compound stephanoporate film, contains mass percent in the film and be 75%～95% NiO, 5%～25% nano metal Ag.
The preparation method of the negative material of film lithium ion battery, its step is as follows:
1) the nickel foam substrate is placed 1mol/L NiSO
4Solution, 0.25mol/L K
2S
2O
8In the mixed solution of solution, concentrated ammonia liquor and water, NiSO
4Solution, K
2S
2O
8The volume ratio of solution, concentrated ammonia liquor and water is 4: 3: 1: 2, take out behind 0.2～5h in 10～60 ℃ of depositions, washing is dry, and in argon gas atmosphere in 350 ℃ of calcinings, obtain foamed nickel supported NiO nano-porous film;
2) be mixing in 1: 1 by volume with the silver ammino solution of 0.005～0.02mol/L and the polyvinylpyrrolidone ethanolic solution of 10～50g/L, substrate after will calcining then places this mixed solution, continue deposition 5～30h at 70 ℃, get foamed nickel supported NiO/Ag nano compound stephanoporate film.
Beneficial effect of the present invention is:
The loose structure of the foamed nickel supported NiO/Ag nano compound stephanoporate of the present invention film has increased the contact interface of active material and electrolyte, the nanometer Ag Dispersion of Particles is in the NiO film, reduced the electric charge transfger impedance, thereby under high magnification, still had high area specific capacity and good cycle performance even guaranteed this negative pole.Adopt the film lithium ion battery non-environmental-pollution of this negative material preparation, can be used for fields such as smart card, CMOS integrated circuit and MEMS (micro electro mechanical system).
Embodiment
Embodiment 1:
1) the nickel foam substrate is placed contains 40mL 1mol/L NiSO
4Solution, 30mL 0.25mol/L K
2S
2O
8In the mixed solution of solution, 10mL concentrated ammonia liquor and 20mL water, stir behind 15 ℃ of deposition 1h, take out down and washing dry, and under the argon gas atmosphere protection in 350 ℃ of calcining 2h.
2) silver ammino solution of 50mL 0.006mol/L and the polyvinylpyrrolidone ethanolic solution of 50mL 12g/L are mixed, the substrate after will calcining then places this mixed solution, continues deposition 24h at 70 ℃, gets foamed nickel supported NiO/Ag nano compound stephanoporate film.
This film thickness is 1 μ m, and the about 200nm in aperture in the film contains mass percent and be 90% NiO and 10% Ag.The reversible capacity of this negative pole under the current density of 2/3C, 2C and 4C is respectively 0.48mAh/cm
2, 0.45mAh/cm
2And 0.42mAh/cm
2The capacity that circulates after 50 times under these current densities is respectively 0.37mAh/cm
2, 0.3mAh/cm
2And 0.28mAh/cm
2
Embodiment 2:
1) the nickel foam substrate is placed contains 40mL 1mol/L NiSO
4Solution, 30mL 0.25mol/L K
2s
2O
8In the mixed solution of solution, 10mL concentrated ammonia liquor and 20mL water, stir behind 25 ℃ of deposition 3h, take out down and washing dry, and under the argon gas atmosphere protection in 350 ℃ of calcining 3h.
2) silver ammino solution of 50mL 0.01mol/L and the polyvinylpyrrolidone ethanolic solution of 50mL 20g/L are mixed, the substrate after will calcining then places this mixed solution, continues deposition 24h at 70 ℃, gets foamed nickel supported NiO/Ag nano compound stephanoporate film.
This film thickness is 2 μ m, and the about 200nm in aperture in the film contains mass percent and be 87% NiO and 13% Ag.The reversible capacity of this negative pole under the current density of 2/3C, 2C and 4C is respectively 1.02mAh/cm
2, 0.93mAh/cm
2And 0.8mAh/cm
2The capacity that circulates after 50 times under these current densities is respectively 0.62mAh/cm
2, 0.47mAh/cm
2And 0.37mAh/cm
2
Embodiment 3:
1) the nickel foam substrate is placed contains 40mL 1mol/L NiSO
4Solution, 30mL 0.25mol/L K
2S
2O
8In the mixed solution of solution, 10mL concentrated ammonia liquor and 20mL water, stir behind 50 ℃ of deposition 2h, take out down and washing dry, and under the argon gas atmosphere protection in 350 ℃ of calcining 2h.
2) silver ammino solution of 50mL 0.02mol/L and the polyvinylpyrrolidone ethanolic solution of 50mL 40g/L are mixed, the substrate after will calcining then places this mixed solution, continues deposition 24h at 70 ℃, gets foamed nickel supported NiO/Ag nano compound stephanoporate film.
This film thickness is 5 μ m, and the about 200nm in aperture in the film contains mass percent and be 75% NiO and 25% Ag.The reversible capacity of this negative pole under the current density of 2/3C and 2C is respectively 2.1mAh/cm
2And 0.9mAh/cm
2The capacity that circulates after 50 times under these current densities is respectively 0.8mAh/cm
2And 0.3mAh/cm
2
With the foamed nickel supported NiO/Ag nano compound stephanoporate film made negative pole, electrode is formed the bipolar electrode simulated battery with metal lithium sheet (purity is greater than 99.9%) as lithium ion battery.Electrolyte is to contain 1mol/LLiPF
6DEC+EC (volume ratio DEC: EC=7: 3), barrier film polypropylene Celgard2400.The simulated battery assembling process is finished in relative humidity is lower than 1% dry glove box.The simulated battery that assembles adopts the constant current charge-discharge mode after placing 12h, and charging/discharging voltage is 0.1V～3.0V.The reversible embedding lithium capacity and the charge-discharge performance of foamed nickel supported NiO/Ag nano compound stephanoporate film cathode measured in circulation in 25 ± 2 ℃ of environment.
The foamed nickel supported NiO/Ag nano compound stephanoporate film cathode of lithium ion battery of the present invention is compared with traditional NiO film cathode, has the following advantages:
1, the active material load capacity is big, and reversible capacity height and high-rate discharge ability are good.The foamed nickel supported NiO/Ag nano compound stephanoporate of the present invention film is deposition substrate with specific area much larger than the nickel foam of sheet metal, with the NiO thin film deposition on all surface of nickel foam.The thickness of the foamed nickel supported NiO/Ag nano compound stephanoporate of the present invention film is micron order, much larger than traditional NiO film (generally below 500nm).The thin film deposition of micron order thickness in the nickel foam substrate of high-specific surface area, the more active material that so just made base load, thus can satisfy the demand of high-capacity battery.It is a kind of porous film for the advantage of the loose structure of film cathode, porous structure has increased the contact interface of active material and electrolyte, thereby still has high area specific capacity and good cycle performance even guaranteed this thick membrane electrode under high magnification.This has overcome in the conventional films electrode increases the problem that chemical property that thickness brings worsens in order to improve activity substance content.Table 1 has provided the comparison of foamed nickel supported NiO/Ag nano compound stephanoporate film and the traditional NiO film reversible capacity under different multiplying of the embodiment of the invention 1, embodiment 2 and embodiment 3.
Table 1
| Membrane electrode | Reversible capacity (mAh/cm under the different multiplying 2) | ||||
| 1/2C | 2/3C | 1C | 2C | 4C | |
| Embodiment 1 film | - | 0.48 | - | 0.45 | 0.42 |
| Embodiment 2 films | - | 1.02 | - | 0.93 | 0.80 |
| Embodiment 3 films | - | 2.10 | - | 0.90 | - |
| Tradition NiO film | 0.15 | - | 0.27 | 0.27 | - |
2, cycle performance is good.Ag particle size in the foamed nickel supported NiO/Ag nano compound stephanoporate of the present invention film has only 5nm, and has high dispersion.These nanometer Ag particles have formed a conductive network in the NiO film, thereby further strengthened electrically contacting between film self, film and substrate, film and the electrolyte, reduce the electric charge transfger impedance, thereby can further improve the chemical property of film.Table 2 provided the foamed nickel supported NiO/Ag nano compound stephanoporate film of the embodiment of the invention 1, embodiment 2 and embodiment 3 and traditional NiO film under different multiplying, circulate after 50 weeks Capacity Ratio.
Table 2
| Membrane electrode | Capacity (mAh/cm under the different multiplying after 50 weeks of circulation 2) | ||||
| 1/2C | 2/3C | 1C | 2C | 4C | |
| Embodiment 1 film | - | 0.37 | - | 0.30 | 0.28 |
| Embodiment 2 films | - | 0.62 | - | 0.47 | 0.37 |
| Embodiment 3 films | - | 0.80 | - | 0.30 | - |
| Tradition NiO film | 0.12 | - | 0.10 | 0.14 | - |
The foamed nickel supported NiO/Ag nano compound stephanoporate film cathode of lithium ion battery of the present invention is compared with traditional NiO film cathode, under the high power charging-discharging electric current, has higher reversible capacity and better cycle ability.
Claims (1)
1. the negative material of film lithium ion battery is characterized in that it is foamed nickel supported NiO/Ag nano compound stephanoporate film, contains mass percent in the film and be 75%～95% NiO, 5%～25% nano metal Ag; Its preparation process is as follows:
1) the nickel foam substrate is placed 1mol/L NiSO
4Solution, 0.25mol/L K
2S
2O
8In the mixed solution of solution, concentrated ammonia liquor and water, NiSO
4Solution, K
2S
2O
8The volume ratio of solution, concentrated ammonia liquor and water is 4: 3: 1: 2, take out behind 0.2～5h in 10～60 ℃ of depositions, washing is dry, and in argon gas atmosphere in 350 ℃ of calcinings, obtain foamed nickel supported NiO nano-porous film;
2) be mixing in 1: 1 by volume with the silver ammino solution of 0.005～0.02mol/L and the polyvinylpyrrolidone ethanolic solution of 10～50g/L, substrate after will calcining then places this mixed solution, continue deposition 5～30h at 70 ℃, get foamed nickel supported NiO/Ag nano compound stephanoporate film.
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|---|---|---|---|
| CN2008100591129A CN101222047B (en) | 2008-01-14 | 2008-01-14 | Cathode material of thin film lithium ion battery and method for producing the same |
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|---|---|---|---|
| CN2008100591129A CN101222047B (en) | 2008-01-14 | 2008-01-14 | Cathode material of thin film lithium ion battery and method for producing the same |
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|---|---|
| CN101222047A CN101222047A (en) | 2008-07-16 |
| CN101222047B true CN101222047B (en) | 2010-12-29 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013470B (en) * | 2010-11-17 | 2013-01-09 | 哈尔滨工业大学 | Foam metal matrix oxide electrode used in lithium-ion battery cathode and preparation method thereof |
| CN102251267B (en) * | 2011-07-04 | 2013-01-23 | 西北有色金属研究院 | Preparation method of NiO porous membrane |
| CN103400980A (en) * | 2013-07-30 | 2013-11-20 | 浙江大学 | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof |
| CN103578784B (en) * | 2013-10-16 | 2017-02-15 | 安徽师范大学 | Nanometer copper oxide composite material and preparation method thereof and super-capacitor electrode and super-capacitor |
| CN103915649A (en) * | 2014-04-22 | 2014-07-09 | 合肥工业大学 | High-energy-density lithium ion battery and preparation method thereof |
| CN105304885B (en) * | 2014-07-15 | 2019-03-26 | 北京理工大学 | A kind of aluminum secondary battery vanadium oxide positive electrode materials and preparation method thereof |
| CN105322026B (en) * | 2015-09-30 | 2018-08-24 | 天津职业技术师范大学 | A kind of NiO:Ag/TiOx diode of heterogenous pn junction |
| CN108063225B (en) * | 2017-12-11 | 2020-07-28 | 合肥国轩电池材料有限公司 | Preparation method of metal/transition metal oxide composite negative electrode material for lithium ion battery |
| CN110607535B (en) * | 2018-06-15 | 2021-07-13 | 新奥科技发展有限公司 | Electrode, preparation method thereof and electrolysis device |
| CN115775883B (en) * | 2023-02-13 | 2023-06-02 | 四川富临新能源科技有限公司 | Surface modification method of lithium iron phosphate positive electrode material |
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