CN110233248A - A kind of high area specific volume cell negative electrode material and its preparation method and application - Google Patents
A kind of high area specific volume cell negative electrode material and its preparation method and application Download PDFInfo
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- CN110233248A CN110233248A CN201910239601.0A CN201910239601A CN110233248A CN 110233248 A CN110233248 A CN 110233248A CN 201910239601 A CN201910239601 A CN 201910239601A CN 110233248 A CN110233248 A CN 110233248A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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Abstract
The invention belongs to energy storage material technical field, specially a kind of high area specific volume cell negative electrode material and its preparation method and application.The material is redox graphene/bismuth composite material；It is using carbon cloth as substrate, using the method for constant voltage electrochemical co-deposition, prepares the composite material of three-dimensional redox graphene and bismuth with fine structure.The composite material has many advantages, such as high carrying capacity, high area specific capacity, high rate capability and high circulation stability；Carbon cloth unit area load capacity is up to 40 mg/cm2；Area specific volume is up to 3.5 mAh/cm2, more than the most of electrode materials reported at present；Capacity is not decayed substantially after 30,000 circle of electrode cycle test, and capacity still has 90% holding after 50,000 circle of circulation；The negative electrode material can be used in flexible water system battery, and after electrode is assembled into full battery with nickel oxyhydroxide material, battery still has 3mAh/cm2Above energy density.Operation of the present invention is simple, consumes energy low, and raw material sources are wide, is easily mass produced.
Description
Technical field
The invention belongs to energy storage material technical fields, and in particular to cell negative electrode material and its preparation method and application.
Background technique
With the development of economy with the sharp increase of world population, world energy sources demand persistently increases, to cause serious
Energy resources race problem and problem of environmental pollution[1].Therefore, in recent years, clean energy resource how is efficiently used to be widely studied,
Including wind energy, solar energy, tide energy etc..Since these energy are intermittent generate, it is therefore desirable to it is converted into electric energy, thus
Further it is used.For this reason, it may be necessary to which the energy storage system for developing highly effective and safe environmental protection more efficiently to utilize energy
Source[2].And energy repeated charge, high-efficient and environmental-friendly secondary cell are then the important research directions of energy storage technology.
Water system battery is the secondary cell using aqueous solution as electrolyte, and it is high to overcome traditional organic system battery electrolyte
Expensive, toxic, the inflammable and explosive, disadvantages such as ionic conductivity is low have many advantages, such as high magnification, environmentally protective.Therefore, water system battery exists
There is important application prospect in the extensive energy storage field of power grid rank[3].Demand day with people to high performance electrode material
Benefit improves, and there is an urgent need to the performances by improving water system battery to the design of energy storage material.
Negative electrode material, such as zinc etc. of the metal usually as water system battery.But zinc holds in the cyclic process of charge and discharge
It is also easy to produce dendrite, to make battery short circuit, cyclical stability is poor[4].It is, thus, sought for other suitable negative electrode materials.Bismuthino
Material has good electric conductivity and suitable negative potential operation interval, is the high-performance negative electrode material with development potentiality.To the greatest extent
The a large amount of explorations of pipe after study, the energy density of bismuthino material is not still able to satisfy actual needs at present[5,6].On the one hand by
Relatively low in the specific discharge capacity of bismuth pole, area specific volume is lower when identical quality electrodes material；On the other hand, work as unit plane
Long-pending carrying capacity improves, and after electrode material thickens, ion diffusion velocity, the transmission speed of electronics of electrode are reduced, so as to cause electricity
The area specific volume of pole is not significantly improved as carrying capacity improves[7].Therefore, develop a kind of bismuthino material with high area specific volume
Preparation method be of great significance for the industrialized production and practical application of electrode material.
Graphite is successfully prepared using the method for mechanical stripping from Univ Manchester UK Novoselov in 2004 et al.
Since alkene[8], in chemical field, physical field and Material Field have started a research boom.Graphene is currently known
The most outstanding material (10 of electric conductivity3~104S/m), theoretical specific surface area is up to 2630 m2/ g, chemical property are stablized, these
Performance outstanding makes graphene have vast potential for future development in energy storage device field.It is above-mentioned with electrode carrying capacity in order to solve
Improve, area specific volume not therewith direct ratio increase the problem of, this project constructs the three-dimensional of graphene using the method for electrochemical deposition
On the one hand back bone network structure improves the carrying capacity of electrode；On the other hand ion diffusion velocity and electron transmission speed are improved.
Summary of the invention
The purpose of the present invention is to provide a kind of high carrying capacity, high-capacitance, have excellent high rate performance and fabulous circulation steady
Qualitative cell negative electrode material and preparation method thereof and the application in flexible water system battery.
High area specific volume cell negative electrode material provided by the invention is the reduction-oxidation graphite with fine three dimensional structure
Alkene/bismuth composite material.The present invention passes through the co-deposition of graphene and bismuth, has constructed the three-dimensional net structure of graphene and bismuth,
And the side wall of three-dimensional net structure (porous structure) is overlapped layer by layer with redox graphene by bismuth and is formed, and is on the one hand improved
The ion-electron transmission efficiency of electrode material and the utilization rate of active material, on the other hand since physics confinement effect improves
The cyclical stability of electrode.
Cell negative electrode material provided by the invention -- redox graphene/bismuth composite material preparation method is specific to walk
It is rapid as follows:
(1) preparation of electroplate liquid
The graphene oxide water solution that volumetric concentration is 0.01 ~ 0.09mg/mL is added in beaker, ethylenediamine tetra-acetic acid is added
Disodium makes 0.1 ~ 0.5mol/L of its concentration, solution is stirred on magnetic stirring apparatus；A certain amount of Bi (NO is added3)3·
5H2O makes 10 ~ 100mmol/L of its concentration, and NaOH solution is added dropwise and adjusts PH to solution clarification；
(2) electro-deposition
Using flexible carbon cloth as working electrode, graphite rod is to electrode, and mercury-mercuric oxide electrode is reference electrode, above-mentioned preparation it is molten
Liquid carries out constant voltage plating as electroplate liquid, and between -0.9V ~ -1.6V, electrode carrying capacity as needed is adjusted electroplating voltage
Electroplating time；Carbon cloth after plating is impregnated in deionized water, surface electrolyte is removed, is then dried in thermal station；
(3) surface coats graphene oxide
By product obtained above, slow dipping is multiple in graphene oxide solution, and sample is dried in thermal station, repeats dipping-
Heat is dry several times to get the graphene-bismuth composite material for arriving cladding graphene oxide.
In step (1), preferably graphene oxide water solution concentration is 0.02 ~ 0.05 mg/mL, more preferably 0.03 mg/
mL；It is preferred that disodium EDTA concentration is 0.2 ~ 0.4 mol/L, more preferably 0.2 mol/L；It is preferred that Bi (NO3)3·
5H2The concentration of O is 20 ~ 70 mmol/L, more preferably 50 mmol/L；It is preferred that solution PH is 4 ~ 7.More preferable solution PH is 5.
In step (2), preferably flexible carbon cloth is working electrode, and constant voltage galvanoplastic electroplating voltage is -1.2V ~ -1.5V,
More preferable electroplating voltage is -1.4V.
In step (3), preferably graphene oxide solution concentration is 3 ~ 8 mg/mL, and more preferable concentration is 5 mg/mL；Slowly
Dipping number is 5 ~ 15 times.Repeating the dry number of dipping-heat is 2 ~ 6 times.
The composite material of graphene and bismuth prepared by the present invention can be used in flexible water system battery as electrode material.
Since the preparation of the electrode material is using the method that electrochemical in-situ deposits on flexible carbon cloth, do not need to add
Enter conductive agent, binder etc. to carry out secondary preparing electrode.Pass through the time of regulation plating, the unit area material load amount of carbon cloth
It can control in 4 to 40 mg/cm2；With the increase of carrying capacity, quality specific volume is held essentially constant；It is tested in three-electrode system
It can obtain, area specific volume is up to 3.5 mAh/cm2, more than the most of electrode materials reported at present.30,000 circle of electrode cycle test
Afterwards, capacity is not decayed substantially, and after 50,000 circle of circulation, capacity still has 90% holding.By the electrode and nickel oxyhydroxide material group
After dressing up full battery, battery still has 3mAh/cm2Above energy density (being calculated according to the quality of negative electrode active material).
The present invention prepares the composite material of graphene and bismuth using the method for electrochemical co-deposition, and obtained composite material is not
Only having three-dimensional net structure, the fine structure being also equipped in network considerably increases the load capacity of active material, and due to
Graphene acts on the confinement of active material, substantially increases the cyclical stability of electrode material.
Preparation method of the present invention is simple, consumes energy low, and raw material sources are wide, is easily mass produced.
Detailed description of the invention
Fig. 1 is redox graphene/bismuth composite material scanning electron microscope (SEM) picture.Wherein, a times magnification
Number is 150 times, and b amplification factor is 20000 times.
Fig. 2 is redox graphene/bismuth composite material X-ray diffraction (XRD) figure.
When Fig. 3 is that graphene oxide concentration is 0.01mg/mL in electroplate liquid, the height of 5 minutes obtained composite materials is electroplated
Amplification factor scanning electron microscope (SEM) picture.
When Fig. 4 is that graphene oxide concentration is 0.03mg/mL in electroplate liquid, the height of 5 minutes obtained composite materials is electroplated
Amplification factor scanning electron microscope (SEM) picture.
When Fig. 5 is that graphene oxide concentration is 0.06mg/mL in electroplate liquid, the height of 5 minutes obtained composite materials is electroplated
Amplification factor scanning electron microscope (SEM) picture.
When Fig. 6 is that graphene oxide concentration is 0.09mg/mL in electroplate liquid, the height of 5 minutes obtained composite materials is electroplated
Amplification factor scanning electron microscope (SEM) picture.
Fig. 7 be different graphene oxide concentration in plating obtained electrode material under open-circuit voltage (- 0.05V) impedance
Spectrogram.
Fig. 8 be different graphene oxide concentration in plating obtained electrode material under operating voltage (- 0.68V) impedance
Spectrogram.
Fig. 9 is the ion diffusion resistance and reaction resistance that obtained electrode material is electroplated in different graphene oxide concentration
Comparison diagram.
Figure 10 is the redox graphene/bismuth obtained in the case where graphene oxide concentration is the plating conditions of 0.03 mg/mL
(current density is 20 mA/cm to discharge curve of the composite material under different carrying capacity2)。
Figure 11 is graphene oxide/bismuth composite material under different current densities, the area specific capacity of electrode material with
The curve of carrying capacity variation.
Figure 12 is redox graphene/bismuth composite material cycle life curve.
Figure 13 is nickel bismuth battery area capacity curve figure under different current densities.
Specific embodiment
(1) preparation of electroplate liquid
The graphene oxide water solution that 40 mL concentration are 0.01M, 0.03 M, 0.06 M, 0.09M is added in 50mL beaker, adds
The disodium ethylene diamine tetraacetate (0.1 M, 0.2 M, 0.5 M) for entering certain mass, after stirring into solution on magnetic stirring apparatus, adds
Enter Bi (NO3)3·5H2O(10 mmol/L, 20 mmol/L, 50mmol/L), PH to 5 or so is adjusted with NaOH solution.
(2) electro-deposition
Using flexible carbon cloth as working electrode, graphite rod is to electrode, and mercury-mercuric oxide electrode is reference electrode, the electricity of above-mentioned preparation
Plating solution carries out constant voltage plating as electroplate liquid.Electroplating voltage is -0.9V, -1.2V-1.4V, electrode carrying capacity tune as needed
Electroplating time is saved between 2 minutes to 15 minutes.Carbon cloth after plating is impregnated in deionized water after removing surface electrolyte,
It is dried in thermal station.
(3) surface cladding graphene oxide processing
By the sample obtained after annealing concentration be 2,5, slowly dipping is multiple in the graphene oxide solution of 10mg/mL, in heat
Sample is dried on platform, is repeated dipping-heat and is done, obtains graphene/bismuth composite material electrode of cladding graphene oxide.
The preparation method of graphene oxide used in the present invention is Hummers method.
Bibliography
[1] T. Lin, I. W. Chen, F. Liu, C. Yang, H. Bi, F. Xu, F. Huang, Science
2015,350, 1508–1513.
[2] D. Larcher and J. M. Tarascon,Nature chemistry2015, 7, 19-29.
[3] H. Kim, J. Hong, K. Y. Park, H. Kim, S. W. Kim,and K. Kang, Chem. Rev
2014, 114, 11788−11827.
[4] J. F. Parker,C. N. Chervin, I. R. Pala, M. Machler, M. F. Burz, J. W.
Long and D. R. Rolison, Science2017, 356, 415–418.
[5] Y. Zeng, Z. Lin, Y. Meng,Y. Wang, M. Yu, X. Lu, and Y. Tong. Advanced Materials2016, 28, 9188-9195.
[6] X. Li, C. Guan, Y. Hu and J. Wang, ACS Appl. Mater. Interfaces2017,9, 26008-26015.
[7] H. Sun, L. Mei, J. Liang, Z. Zhao, C. Lee, H. Fei, M.Ding, J. Lau, M.
Li, C. Wang, X. Xu, G. Hao, B. Papandrea, I. Shakir, B.Dunn, Y. Huang, and X.
Duan, Science2017, 356, 599–604.
[8] K. S. Novoselov,A. K. Geim, S. V. Morozov,D. Jiang,Y. Zhang, S. V.
Dubonos, I. V. Grigorieva, A. A. Firsov, Science2004, 306, 666–669.。
Claims (6)
1. a kind of preparation method of cell negative electrode material, the cell negative electrode material is redox graphene/bismuth composite wood
Material, specific step is as follows for preparation:
(1) preparation of electroplate liquid
The graphene oxide water solution that volumetric concentration is 0.01 ~ 0.09mg/mL is added in beaker, ethylenediamine tetra-acetic acid is added
Disodium makes 0.1 ~ 0.5mol/L of its concentration, solution is stirred on magnetic stirring apparatus；A certain amount of Bi (NO is added3)3·
5H2O makes 10 ~ 100mmol/L of its concentration, and NaOH solution is added dropwise and adjusts PH to solution clarification；
(2) electro-deposition
Using flexible carbon cloth as working electrode, graphite rod is to electrode, and mercury-mercuric oxide electrode is reference electrode, above-mentioned preparation it is molten
Liquid carries out constant voltage plating as electroplate liquid, and for electroplating voltage between -0.9V ~ -1.6V, electrode carrying capacity as needed adjusts electricity
Plate the time；Carbon cloth after plating is impregnated in deionized water, surface electrolyte is removed, is then dried in thermal station；
(3) surface coats graphene oxide
By product obtained above, slow dipping is multiple in graphene oxide solution, and sample is dried in thermal station, repeats dipping-
Heat is dry several times to get the graphene-bismuth composite material for arriving cladding graphene oxide.
2. preparation method according to claim 1, which is characterized in that in step (1), graphene oxide water solution concentration
For 0.02 ~ 0.05 mg/mL；Disodium EDTA concentration is 0.2 ~ 0.4 mol/L；Bi(NO3)3·5H2The concentration of O
For 20 ~ 70 mmol/L；Solution PH is 4 ~ 7.
3. preparation method according to claim 1, which is characterized in that in step (2), flexible carbon cloth is working electrode, permanent
Voltage galvanoplastic electroplating voltage is -1.2V ~ -1.5V.
4. preparation method according to claim 1, which is characterized in that in step (3), graphene oxide solution concentration is 3
~8 mg/mL；Slow dipping number is 5 ~ 15 times；Repeating the dry number of dipping-heat is 2 ~ 6 times.
5. the cell negative electrode material that the preparation method as described in one of claim 1-4 obtains is that redox graphene/bismuth is compound
Material has fine three dimensional structure, and the side wall of three-dimensional net structure is overlapped layer by layer with redox graphene by bismuth and formed.
6. application of the cell negative electrode material as claimed in claim 5 in flexible water system battery.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113130873A (en) * | 2021-05-20 | 2021-07-16 | 武汉科技大学 | Porous bismuth-carbon material, preparation method and application thereof |
| CN113258025A (en) * | 2021-05-07 | 2021-08-13 | 西北工业大学 | Bismuth-based negative electrode for high-performance water-based battery and preparation method |
| CN113871593A (en) * | 2021-09-26 | 2021-12-31 | 西安热工研究院有限公司 | Ag-Cu2O-RGO lithium ion battery cathode material and preparation method thereof |
| CN114032672A (en) * | 2021-11-08 | 2022-02-11 | 四川大学 | Carbon fiber modified by controllable reduced graphene oxide and application thereof |
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| CN103811763A (en) * | 2012-11-13 | 2014-05-21 | 海洋王照明科技股份有限公司 | Graphene-bismuth oxide composite material as well as preparation method thereof, lead carbon battery cathode diachylon as well as preparation method thereof and lead carbon battery cathode plate |
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| CN108400292A (en) * | 2018-01-24 | 2018-08-14 | 东北电力大学 | A kind of preparation method and applications of bismuth simple substance nanometer sheet combination electrode |
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| CN103811763A (en) * | 2012-11-13 | 2014-05-21 | 海洋王照明科技股份有限公司 | Graphene-bismuth oxide composite material as well as preparation method thereof, lead carbon battery cathode diachylon as well as preparation method thereof and lead carbon battery cathode plate |
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| CN108400292A (en) * | 2018-01-24 | 2018-08-14 | 东北电力大学 | A kind of preparation method and applications of bismuth simple substance nanometer sheet combination electrode |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113258025A (en) * | 2021-05-07 | 2021-08-13 | 西北工业大学 | Bismuth-based negative electrode for high-performance water-based battery and preparation method |
| CN113258025B (en) * | 2021-05-07 | 2023-02-28 | 西北工业大学 | Bismuth-based negative electrode for high-performance water-based battery and preparation method |
| CN113130873A (en) * | 2021-05-20 | 2021-07-16 | 武汉科技大学 | Porous bismuth-carbon material, preparation method and application thereof |
| CN113871593A (en) * | 2021-09-26 | 2021-12-31 | 西安热工研究院有限公司 | Ag-Cu2O-RGO lithium ion battery cathode material and preparation method thereof |
| CN114032672A (en) * | 2021-11-08 | 2022-02-11 | 四川大学 | Carbon fiber modified by controllable reduced graphene oxide and application thereof |
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