CN102709534A - Sodion battery cathode material - Google Patents
Sodion battery cathode material Download PDFInfo
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- CN102709534A CN102709534A CN2012102028267A CN201210202826A CN102709534A CN 102709534 A CN102709534 A CN 102709534A CN 2012102028267 A CN2012102028267 A CN 2012102028267A CN 201210202826 A CN201210202826 A CN 201210202826A CN 102709534 A CN102709534 A CN 102709534A
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- sodium
- ion
- ion battery
- negative material
- battery negative
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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 a sodion battery cathode material, which is an ion-doped carbon material, wherein the carbon material is from pyrolytic carbon of various organic matter materials; the prepared carbon material has the ion doping property and can provide a suitable sodion de-intercalation channel; and the sodion battery cathode material has reversible sodion de-intercalation performance and is very hopeful to become a sodion battery cathode material which is low in cost and environment-friendly.
Description
Technical field
The present invention relates to one type of sodium-ion battery negative material, belong to energy storage material and secondary battery technology.
Background technology
Along with the development of society and continuing to increase of the size of population, the energy demand in the whole world improves constantly, and the consumption of fossil energy is soaring year by year thereupon.The strong energy resource structure that relies on fossil energy is brought the problem of two aspects to social development, and the one, fossil energy can't be regenerated in a short time, causes the energy shortage problem serious day by day; The 2nd, caused greenhouse effect of the lot of consumption of fossil energy and problem of environmental pollution are on the rise.Therefore, solve the resource and environment problem and become the two big important topics that concern human social.Obviously, development and utilization regenerative resource energetically like solar energy, wind energy, geothermal energy, tidal energy etc., is progressively broken away from human dependence to fossil energy, is the unique possibility approach that promotes social sustainable development.Yet these regenerative resources all need be developed and build supporting apparatus for storing electrical energy (being energy-accumulating power station) and guaranteed the continuity and the stability of generating electricity, supplying power.In present energy storage system, chemical energy-storage battery is an extensive energy storage device the most likely owing to have flexibility, high efficiency and do not have the region restriction.
Lithium ion battery has obtained develop rapidly as high specific energy battery system in portable type electronic product, electric tool and electric automobile field.Yet, receive the restriction of lithium resource, possibly can't support the development of extensive accumulation power supply.Therefore, development resource is abundant, and advanced battery system with low cost is to solve the inevitable outlet that following extensive accumulate is used.Sodium element and lithium are in same main group, and chemical property is similar, and electrode potential is also more approaching, and the aboundresources of sodium, and it is low to refine cost.If substitute lithium with sodium, develop the sodium-ion battery of excellent working performance, will have the competitive advantage bigger than lithium ion battery.Therefore, the storage sodium electrode material of seeking high power capacity and excellent cycle performance has become the current battery hot research fields.
For embedding sodium positive electrode, some feasible report so far, as contain the sodium transition metal oxide (like NaxCoO
2, NaxMnO
2, NaNi
0.5Mn
0.5O
2) and transition metal fluorophosphoric acid sodium salt (like NaVPO
4F, Na
2FePO
4F).But then studying lessly relatively for embedding sodium negative material, mainly is that to be limited to the graphite material interlamellar spacing (0.335 nanometer) with good embedding lithium performance less, can't effectively embed and deviate from than the sodium ion of heavy ion radius.Therefore, realize that reversible sodium ion embeds and deviates from, the material with carbon element that preparation has than large interlamellar spacing is crucial.
Summary of the invention
Technical problem to be solved by this invention provides one type of RESEARCH OF PYROCARBON material with ion doping as the sodium-ion battery negative material.This RESEARCH OF PYROCARBON makes the embedding of its suitable sodium ion and deviates from because ion doping can be regulated the carbon-coating spacing and change chemical environment.Experiment shows that this type material all has good reversible sodium ion and takes off the embedding performance, has higher reversible capacity and better cycle performance.
Technical scheme of the present invention is:
One type of sodium-ion battery negative material, for having the material with carbon element of ion doping, dopant ion is meant the nonmetalloid that is different from carbon, oxygen, hydrogen; The material with carbon element of described ion doping is made by organic matter pyrolysis, and pyrolytical condition is in inert atmosphere, and 600 ~ 1600
oCarbonization is 2 ~ 24 hours under the C.
In the such scheme, the organic substance self that dopant ion can come from pyrolysis has, like polyaniline, polyvinyl chloride, polypyrrole, polythiophene, sucrose, glucose and their derivative; Or in pyrolytic process, add doped chemical.
Described dopant ion is meant in material with carbon element, to have nonmetalloid different and carbon, oxygen, hydrogen, like one or more the combination in nitrogen, sulphur, phosphorus, boron, chlorine, fluorine, bromine, iodine, the silicon.
Described inert atmosphere is nitrogen or argon gas.
The present invention also provides a kind of sodium-ion battery, by negative pole, and positive pole, electrolyte and barrier film are formed, and described negative material is by the material with carbon element of above-mentioned ion doping.
Show that through electro-chemical test the material with carbon element with ion doping that proposes in the patent of the present invention has good sodium ion embedding and takes off ability; And the preparation method is simple; Abundant raw material, with low cost, be expected to very much become a kind of sodium-ion battery negative material of practicability.
Description of drawings
Fig. 1, be first all charging and discharging curves of the polyvinyl chloride RESEARCH OF PYROCARBON of the embodiment of the invention 1.
Fig. 2, be the cycle performance curve of the polyvinyl chloride RESEARCH OF PYROCARBON of the embodiment of the invention 1.
Fig. 3, be the charging and discharging curve of the polythiophene RESEARCH OF PYROCARBON of the embodiment of the invention 1.
Fig. 4, be the cycle performance curve of the polythiophene RESEARCH OF PYROCARBON of the embodiment of the invention 2.
Embodiment
Embodiment 1. polyvinyl chloride RESEARCH OF PYROCARBON and electrochemistry storage sodium performance
Pvc material is positioned in the high temperature furnace that is full of nitrogen, 600
oC pyrolysis 6h.The gained material with carbon element mixes the weight ratio of pressing 90:5:5 with vinylidene (PVDF) (being dissolved in the N methyl pyrrolidone), acetylene black even, applies into electrode film.With this electrode film is work electrode, and the sodium metal sheet is to electrode, 1mol L
-1NaPF
6(EC-DEC=1:1) for electrolyte is assembled into its chemical property of battery testing, Fig. 1 is the constant current charge-discharge curve of polyvinyl chloride RESEARCH OF PYROCARBON. as shown in Figure 1 at 50 mA g
-1Under the current density, the reversible capacity of material is 200mAh g
-1Battery circulated after 100 weeks, and capacity still keeps 90 %.(Fig. 2)
The preparation of embodiment 2. polythiophene RESEARCH OF PYROCARBON materials and storage sodium performance
The polythiophene material is positioned in the high temperature furnace that is full of nitrogen, 1200
oC pyrolysis 10h, the material with carbon element of gained mix the weight ratio of pressing 90:5:5 with vinylidene (PVDF) (being dissolved in the N methyl pyrrolidone), acetylene black even, applies into electrode film.With this electrode film is work electrode, and the sodium metal sheet is to electrode, 1mol L
-1NaPF
6(EC-DEC=1:1) for electrolyte is assembled into its chemical property of battery testing, Fig. 3 is the constant current cycle performance curve of phenolic resins pyrolysis carbon, and current density is 50 mA g
-1, charging and discharging voltage range is 2.0 ~ 0V (Na
+/ Na).The reversible capacity of this material as shown in Figure 3 is 170mAh g
-1Fig. 4 is the cyclic curve of this material.Capacity still keeps 130 mAh g after 80 weeks of circulation
-1
The preparation of embodiment 3. polyaniline RESEARCH OF PYROCARBON and storage sodium performance
Polyaniline material is positioned in the high temperature furnace that is full of nitrogen, 1000
oC pyrolysis 6h, the material with carbon element of gained mix the weight ratio of pressing 90:5:5 with vinylidene (PVDF) (being dissolved in the N methyl pyrrolidone), acetylene black even, applies into electrode film.With this electrode film is work electrode, and the sodium metal sheet is to electrode, 1mol L
-1NaPF
6(EC-DEC=1:1) for electrolyte is assembled into its chemical property of battery testing, current density is 50 mA g
-1, charging and discharging voltage range is 1.2 ~ 0V (Na
+/ Na).Reversible capacity through test material is 250 mAh g
-1, capacity still keeps 220 mAh g after 100 weeks of circulation
-1
The preparation of embodiment 4. P doping sucrose RESEARCH OF PYROCARBON and storage sodium performance
Sucrose and phosphoric acid are mixed by the 98:2 mass ratio, be positioned in the high temperature furnace that is full of argon gas gas, 800
oC pyrolysis 24h, the material with carbon element of gained mix the weight ratio of pressing 90:5:5 with vinylidene (PVDF) (being dissolved in the N methyl pyrrolidone), acetylene black even, applies into electrode film.With this electrode film is work electrode, and the sodium metal sheet is to electrode, 1mol L
-1NaPF
6(EC-DEC=1:1) for electrolyte is assembled into its chemical property of battery testing, current density is 50 mA g
-1, charging and discharging voltage range is 1.2 ~ 0V (Na
+/ Na).Reversible capacity through test material is 185mAh g
-1, capacity still keeps 140 mAh g after 100 weeks of circulation
-1
The preparation of embodiment 5. B doping glucose RESEARCH OF PYROCARBON and storage sodium performance
Glucose and boric acid are mixed by the 99:1 mass ratio, be positioned in the high temperature furnace that is full of argon gas gas, 1600
oC pyrolysis 2h, the material with carbon element of gained mix the weight ratio of pressing 90:5:5 with vinylidene (PVDF) (being dissolved in the N methyl pyrrolidone), acetylene black even, applies into electrode film.With this electrode film is work electrode, and the sodium metal sheet is to electrode, 1mol L
-1NaPF
6(EC-DEC=1:1) for electrolyte is assembled into its chemical property of battery testing, current density is 50 mA g
-1, charging and discharging voltage range is 1.2 ~ 0V (Na
+/ Na).Reversible capacity through test material is 210mAh g
-1
Claims (7)
1. one type of sodium-ion battery negative material is characterized in that, for having the material with carbon element of ion doping, dopant ion is meant the nonmetalloid that is different from carbon, oxygen, hydrogen; The material with carbon element of described ion doping is made by organic matter pyrolysis, and pyrolytical condition is in inert atmosphere, and 600 ~ 1600
oCarbonization is 2 ~ 24 hours under the C.
2. sodium-ion battery negative material according to claim 1 is characterized in that, the organic substance self that dopant ion comes from pyrolysis has.
3. sodium-ion battery negative material according to claim 2 is characterized in that, the organic substance of pyrolysis is polyaniline, polyvinyl chloride, polypyrrole, polythiophene, sucrose, glucose or their derivative.
4. sodium-ion battery negative material according to claim 1 is characterized in that, dopant ion comes from and in pyrolytic process, adds doped chemical.
5. sodium-ion battery negative material according to claim 1 is characterized in that, described dopant ion is meant one or more the combination in nitrogen, sulphur, phosphorus, boron, chlorine, fluorine, bromine, iodine, the silicon.
6. sodium-ion battery negative material according to claim 1 is characterized in that, described inert atmosphere is nitrogen or argon gas.
7. sodium-ion battery, by negative pole, positive pole, electrolyte and barrier film are formed, and described negative material is by the material with carbon element of the described ion doping of claim 1～6.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104043469A (en) * | 2014-01-06 | 2014-09-17 | 北京化工大学 | Nitrogen-doped carbon black catalyst and its preparation method and use |
| CN104103835A (en) * | 2014-07-10 | 2014-10-15 | 华中科技大学 | Cathode material for sodium ion battery, and preparation method of cathode material |
| CN104269526A (en) * | 2014-09-19 | 2015-01-07 | 易高环保能源研究院有限公司 | Preparation of polyacrylonitrile/lignin carbon nanofiber electrode for sodium ion battery |
| CN105024056A (en) * | 2015-06-05 | 2015-11-04 | 中南大学 | Bismuth/nitrogen-doped carbon-sphere composite anode material for sodium ion battery and preparation method thereof |
| CN105390674A (en) * | 2015-10-29 | 2016-03-09 | 中南大学 | Iron diselenide/sulfur-doped graphene anode composite material for sodium-ion battery and preparation method of iron diselenide/sulfur-doped graphene anode composite material |
| CN106299368A (en) * | 2016-07-23 | 2017-01-04 | 天津大学 | A kind of method preparing N doping cellular disordered carbon material |
| CN106711410A (en) * | 2016-12-02 | 2017-05-24 | 北京理工大学 | Battery negative electrode material and preparation method thereof as well as sodium-ion battery |
| CN106972162A (en) * | 2017-04-21 | 2017-07-21 | 复旦大学 | A kind of sodium-ion battery double-doped hard carbon microballoon of negative material phosphorus sulphur and preparation method thereof |
| CN106997810A (en) * | 2017-03-15 | 2017-08-01 | 温州大学 | A kind of nitrogen, phosphorus, chlorine co-doped carbon material, preparation method and the usage |
| CN108428894A (en) * | 2018-02-09 | 2018-08-21 | 武汉科技大学 | A kind of sulfur doping two dimension carbon material, preparation method and application |
| CN109713287A (en) * | 2019-01-02 | 2019-05-03 | 齐鲁工业大学 | A kind of preparation method of the derivative sulfur doping carbon anode material of lithium-ion battery of polythiophene |
| CN111235696A (en) * | 2020-01-21 | 2020-06-05 | 南京航空航天大学 | Bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material for sodium ion battery, preparation method of bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material and sodium ion battery |
| CN111254282A (en) * | 2020-02-05 | 2020-06-09 | 东华理工大学 | Preparation method of polypyrrole/phosphorus-doped graphitized carbon composite conductive membrane electrode |
| CN111682173A (en) * | 2020-06-03 | 2020-09-18 | 湖南大学 | Composite material of multi-heteroatom co-doped carbon shell coated silicon and preparation method thereof |
| CN112794365A (en) * | 2021-01-05 | 2021-05-14 | 西南大学 | Phosphorus-doped conductive carbon-coated metal oxide composite material, preparation method thereof and application thereof in sodium-ion battery cathode material |
| CN114583137A (en) * | 2022-03-17 | 2022-06-03 | 华中科技大学 | Method for modifying carbon surface by doping sulfur with phosphorus and application thereof |
| TWI827205B (en) * | 2022-08-18 | 2023-12-21 | 台灣立凱電能科技股份有限公司 | Dual-cation metal battery and charging and discharging method thereof |
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Cited By (28)
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|---|---|---|---|---|
| CN104043469A (en) * | 2014-01-06 | 2014-09-17 | 北京化工大学 | Nitrogen-doped carbon black catalyst and its preparation method and use |
| CN104043469B (en) * | 2014-01-06 | 2017-10-27 | 北京化工大学 | A kind of nitrating carbon black catalyst and its preparation method and application |
| CN104103835A (en) * | 2014-07-10 | 2014-10-15 | 华中科技大学 | Cathode material for sodium ion battery, and preparation method of cathode material |
| CN104103835B (en) * | 2014-07-10 | 2017-01-11 | 华中科技大学 | Cathode material for sodium ion battery, and preparation method of cathode material |
| CN104269526A (en) * | 2014-09-19 | 2015-01-07 | 易高环保能源研究院有限公司 | Preparation of polyacrylonitrile/lignin carbon nanofiber electrode for sodium ion battery |
| CN105024056B (en) * | 2015-06-05 | 2017-04-05 | 中南大学 | A kind of sodium-ion battery bismuth/nitrating carbon ball anode material and preparation method thereof |
| CN105024056A (en) * | 2015-06-05 | 2015-11-04 | 中南大学 | Bismuth/nitrogen-doped carbon-sphere composite anode material for sodium ion battery and preparation method thereof |
| CN105390674B (en) * | 2015-10-29 | 2018-02-23 | 中南大学 | A kind of two ferrous selenides of sodium-ion battery/sulfur doping graphene anode material and preparation method thereof |
| CN105390674A (en) * | 2015-10-29 | 2016-03-09 | 中南大学 | Iron diselenide/sulfur-doped graphene anode composite material for sodium-ion battery and preparation method of iron diselenide/sulfur-doped graphene anode composite material |
| CN106299368A (en) * | 2016-07-23 | 2017-01-04 | 天津大学 | A kind of method preparing N doping cellular disordered carbon material |
| CN106711410A (en) * | 2016-12-02 | 2017-05-24 | 北京理工大学 | Battery negative electrode material and preparation method thereof as well as sodium-ion battery |
| CN106711410B (en) * | 2016-12-02 | 2019-07-02 | 北京理工大学 | Cell negative electrode material and preparation method thereof and sodium-ion battery |
| CN106997810A (en) * | 2017-03-15 | 2017-08-01 | 温州大学 | A kind of nitrogen, phosphorus, chlorine co-doped carbon material, preparation method and the usage |
| CN106997810B (en) * | 2017-03-15 | 2019-11-15 | 温州大学 | A kind of nitrogen, phosphorus, chlorine co-doped carbon material, preparation method and the usage |
| CN106972162A (en) * | 2017-04-21 | 2017-07-21 | 复旦大学 | A kind of sodium-ion battery double-doped hard carbon microballoon of negative material phosphorus sulphur and preparation method thereof |
| CN108428894B (en) * | 2018-02-09 | 2020-08-11 | 武汉科技大学 | Sulfur-doped two-dimensional carbon material, and preparation method and application thereof |
| CN108428894A (en) * | 2018-02-09 | 2018-08-21 | 武汉科技大学 | A kind of sulfur doping two dimension carbon material, preparation method and application |
| CN109713287A (en) * | 2019-01-02 | 2019-05-03 | 齐鲁工业大学 | A kind of preparation method of the derivative sulfur doping carbon anode material of lithium-ion battery of polythiophene |
| CN109713287B (en) * | 2019-01-02 | 2022-02-01 | 齐鲁工业大学 | Polythiophene derived sulfur-doped carbon sodium ion battery negative electrode material |
| CN111235696A (en) * | 2020-01-21 | 2020-06-05 | 南京航空航天大学 | Bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material for sodium ion battery, preparation method of bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material and sodium ion battery |
| CN111254282A (en) * | 2020-02-05 | 2020-06-09 | 东华理工大学 | Preparation method of polypyrrole/phosphorus-doped graphitized carbon composite conductive membrane electrode |
| CN111254282B (en) * | 2020-02-05 | 2021-11-09 | 东华理工大学 | Preparation method of polypyrrole/phosphorus-doped graphitized carbon composite conductive membrane electrode |
| CN111682173A (en) * | 2020-06-03 | 2020-09-18 | 湖南大学 | Composite material of multi-heteroatom co-doped carbon shell coated silicon and preparation method thereof |
| CN111682173B (en) * | 2020-06-03 | 2021-12-07 | 湖南大学 | Composite material of multi-heteroatom co-doped carbon shell coated silicon and preparation method thereof |
| CN112794365A (en) * | 2021-01-05 | 2021-05-14 | 西南大学 | Phosphorus-doped conductive carbon-coated metal oxide composite material, preparation method thereof and application thereof in sodium-ion battery cathode material |
| CN114583137A (en) * | 2022-03-17 | 2022-06-03 | 华中科技大学 | Method for modifying carbon surface by doping sulfur with phosphorus and application thereof |
| CN114583137B (en) * | 2022-03-17 | 2023-10-24 | 华中科技大学 | Method for modifying carbon surface by sulfur doped phosphorus and application thereof |
| TWI827205B (en) * | 2022-08-18 | 2023-12-21 | 台灣立凱電能科技股份有限公司 | Dual-cation metal battery and charging and discharging method thereof |
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Effective date of registration: 20220627 Address after: 518000 room 902, building 6, phase II, Dongjiu Innovation Park, No. 73, xialinan Road, xialilang community, Nanwan street, Longgang District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Jana Energy Technology Co.,Ltd. Address before: 430072 Hubei Province, Wuhan city Wuchang District of Wuhan University Luojiashan Patentee before: WUHAN University |
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