CN100557740C - Ultra-capacitor conductivity titania lithium electrode material with carbon and preparation method thereof - Google Patents
Ultra-capacitor conductivity titania lithium electrode material with carbon and preparation method thereof Download PDFInfo
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- CN100557740C CN100557740C CNB2005100309980A CN200510030998A CN100557740C CN 100557740 C CN100557740 C CN 100557740C CN B2005100309980 A CNB2005100309980 A CN B2005100309980A CN 200510030998 A CN200510030998 A CN 200510030998A CN 100557740 C CN100557740 C CN 100557740C
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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
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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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to the carbon that a kind of battery, electrochemical super-capacitor use and coat lithium titanyl combination electrode material and preparation method.This electrode material body is spinel-type Li
(8x/x+4)Ti
(8/x+4)O
4(wherein x is the mol ratio of Li/Ti, 0.5≤x≤0.8), the bulk material particle surface coats the material with carbon element that one deck has high electron conduction.With this composite material is negative pole, and commercial absorbent charcoal material is the model electrochemical ultra-capacitor of anodal assembling, and its multiplying power and cycle performance all are better than the ultracapacitor that traditional lithium titanyl material is assembled as negative pole.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of carbon and coat lithium titanyl combination electrode material and preparation method thereof.
Background technology
Along with constant development of economy, must cause the aggravation of the exhaustion of petroleum resources and environmental pollution, greenhouse effects of the earth.New forms of energy are economized energy technology, and the development and utilization that reaches the comprehensive high-efficiency rate of Environmental Technology has become very necessary problem, and the development electric automobile is imperative, countries in the world active development fuel cell electric vehicle (FCEV).But (W/Kg) is less for fuel cell output power, can not satisfy starting, quicken and the requirement of climbing, must have extended cycle life with other, and energy density is big and can make the secondary cell or the capacitor bank of large current density.For example Toyota (Toyota) uses the Ni-MH battery, and Honda (Honda) is used electrochemical double layer capacitor, and Mazda (Matsuda) uses lead acid accumulator, and daily output (Nissan) is with the act as a fuel accessory power supply of battery of lithium ion battery.Though secondary cell such as ni-mh, lithium ion has bigger energy density, cycle life is shorter, and high rate during charging-discharging is relatively poor, and its power output is about 600W/kg.Though existing electrochemical double layer capacitor has the long-life, high-output power (for example the ultra-capacitor of Honda fuel-cell vehicle, its power output reaches 1500W/kg), energy density is less than normal.
Calendar year 2001 U.S. Telcordia Technologies (US6252762) has reported that anodal Electrostatic Absorption, the negative pole of anion on activated carbon electrodes of utilizing utilizes embedding in the lithium ion battery/the take off ultra-capacitor of a kind of newtype of embedding reaction, its energy density can reach the tens of watt-hours of per kilogram, mainly is the Li-Ti oxide Li of spinel-type as electrode material
4Ti
5O
12Yet the negative pole Li-Ti oxide in the above-mentioned capacitor system is an insulator, uses very difficulty now as the material of large power, electrically chemical capacitor.
The existing super capacitor anode Li that improves
4Ti
5O
12The method of electrode conductivity mainly is to add a large amount of carbon back electric conducting materials in the batch mixing process, as, electrically conductive graphite, acetylene black, conductive carbon black or the like.This method can be improved the electric conductivity of material largely, makes it to reach the needs of capacitor work.But also there are problems in this method: 1. the adding of a large amount of electric conducting materials causes electrode density to improve.In view of the tap density of lithium titanyl material itself is lower, if add the material with carbon element of a large amount of less denses again, causes negative electrode density to improve, and then reduce the energy density of whole capacitor body system.2. the adding of a large amount of electric conducting materials makes that the binding agent consumption in the capacitor anode preparation process improves greatly.Because common conduction class material with carbon element all has higher specific surface area, mix a large amount of binding agents of consumption in the slurry process at electrode, the too much introducing of binding agent also reduces electrode density on the one hand, also can reduce the electric conductivity of entire electrode on the other hand.3., still can not reach the requirement that capacitor high power rule charges and discharge though the interpolation of external conductive carbon material can improve the electrodes conduct performance.The graphite-like of external interpolation or carbon class electric conducting material are by shear agitation purely with contacting of lithium titanyl body or grind and disperse, the physics contact that forms at last, and negative pole lithium titanyl material itself still is a semiconductor.More than comprehensive, have now and improve and improve super capacitor anode Li
4Ti
5O
12The basic method of electrode conductivity is to improve the electric conductivity of material itself, makes its electric conductivity can improve 1-3 the order of magnitude on the original basis.
For addressing the above problem, the present invention is by using liquid phase or chemical gaseous phase method for coating, surface in lithium titanyl negative pole body granules coats one deck conductive carbon material uniformly, under the prerequisite that does not influence the chemical formula proportioning of material own, improve the electric conductivity of lithium titanyl material, this carbon coats the needs that lithium titanyl combination electrode material can satisfy the ultracapacitor high power discharge.
Summary of the invention
The objective of the invention is to propose a kind of conductivity titania lithium electrode material with carbon and preparation method thereof, to satisfy the application requirements of electric chemical super capacitor.
The conductivity titania lithium electrode material with carbon that the present invention proposes, it is not simply to be mixed with body lithium titanyl material by material with carbon element to form, but at high temperature react the carbon and the bulk material that form by carbon source and bulk material is the form of clad structure, its carbon coating layer combines closely with the lithium titanyl of body, be difficult for peeling off, and this carbon coated has the electron conduction ability, thereby improves the electric conductivity of material.
The body of above-mentioned electrode composite material is spinel-type Li
(8x/x+4)Ti
(8/x+4)O
4, wherein x is the mol ratio of Li/Ti, 0.5≤x≤0.8.
Carbon coating layer can be the surface of all or part of coating lithium titanyl material, part coat refer generally to coat area surpass the body particle surface long-pending 50%, carbon coating layer can contain nano-pore and micropore.
Among the present invention, the carbon content in this composite material should account for the 2%-20% of composite material gross mass, if the carbon coated amount is less than 2%, then because carbon content is low excessively, can't fundamentally improve the electric conductivity of material; If covering amount greater than 20%, then because this part material with carbon element only possesses conductivity and no capacity own, can reduce the capacity of whole composite material so to a great extent.
Among the present invention, the material with carbon element that is coated on this electrode composite material can be an amorphous carbon, be specially micromolecule cracking carbon (as acetylene, methane, benzene, phenolphthalein, borine etc.), polymer cracking carbon is (as polyphenyl, polyvinyl chloride, Kynoar, polyphenylene sulfide, epoxy resin, poly-naphthalene, the polymer that contains benzene skeleton etc., furane resins, acrylonitrile-butadiene--styrene copolymer etc.) a kind of, perhaps by other carbon matrix precursor K cryogenic treatment thing (as petroleum coke, pitch coke, phenolic resins, rice hulls etc.), perhaps be difficult for graphited hard carbon and easy graphited graphitic carbon for what above-mentioned agraphitic carbon managed aloft that the back forms.
Among the present invention, employed carbon method for coating is following three classes: first kind liquid phase coats method, and promptly by body and liquid carbon source (as pitch, PVA etc.) are evenly mixed, then high-temperature process makes body surface coat the method for carbon-coating; Second gas-like phase coats method, is about to bulk material and places high temperature reaction stove, and the employing inert gas is carrier gas, brings the effumability carbon source into reaction vessel, thereby coats the method for carbon-coating at body surface; The 3rd class solid phase carbonization sedimentation is mainly evenly mixed body with solid-state carbon source (phenolic resins, rice hulls etc.), and then high-temperature process makes body surface coat the method for carbon-coating.
Among the preparation method of the present invention, the temperature that chemical gaseous phase coats need be controlled at 700-1000 ℃.The temperature that coats is if be lower than 700 ℃, and then the carbon-coating electric conductivity of the lithium titanyl-graphite combination electrode material of final gained is not good; If temperature of plate is high 1000 ℃, then because the strong reducing property energy of carbon in the time of high temperature, easily make the lithium titanyl material oxygen loss of body, cause the bulk material chemical property partly or entirely to be lost, and bulk material exists in this temperature or when being higher than this temperature, and decompose may.In this method, need control to coat temperature retention time 60-720min, be less than 60min if coat temperature retention time, carbon covering amount lower (＜2%) does not reach the purpose that improves material conductivity; If coat temperature retention time greater than 720min, then the carbon covering amount is too high, makes the material monolithic capacity reduce.
The active carbon that adopts carbon of the present invention to coat lithium titanyl combination electrode material and high-ratio surface is formed asymmetric ultra-capacitor, and its cycle performance and high rate performance all are better than the capacitor system of traditional lithium titanium oxygen compound and active carbon assembling.
Specific implementation method
The present invention is further illustrated by embodiment down.
Embodiment 1:
With Li
4Ti
5O
12Bulk material is as negative material.Capacitor anode is formed according to lithium titanyl (perhaps charcoal coats lithium titanyl composite material): conductive agent 1: conductive agent 2: binding agent=80: 6: 7: 7 mixed slurry, then control certain coating thickness, and evenly be coated on the Copper Foil collector.What the positive electrode active carbon adopted is commercial active carbon, and wet end furnish is according to active carbon: conductive agent: binding agent=mix slurry at 85: 5: 10, and then control certain thickness and coat on the aluminum foil current collector.Among this embodiment, regulation negative material utilance is 60% to control the coating thickness of anodal negative pole.Then two kinds of electrodes are cut according to specification, matched group dress up the 7# capacitor (φ 10*38L, mm), the barrier film that is adopted is the commercial li-ion battery diaphragm, electrolyte is the commercial li-ion battery liquid electrolyte.The capacitor operation interval is 1.0V-3.0V.This embodiment is a Comparative Examples, and the negative material electric conductivity is relatively poor, so cycle life of capacitor own and multiplying power performance are all not good.Especially it is when 30C discharges, and condenser capacity is 4.9m Ah (seeing table .1 for details).
Embodiment 2:
With Li
4Ti
5O
12Material is a body, places tube furnace.With toluene is carbon source, and Ar gas is as source of the gas, and the control gaseous flow blasts the toluene steam in the tube furnace, and tube furnace temperature programming therebetween is to 900 ℃ of reaction temperatures, treats that furnace temperature reaches to cause temperature requiredly, and the control furnace temperature is at reaction temperature 300min.After cooling, through grinding, promptly get required carbon and coat lithium titanyl combination electrode material, carbon content is 5% in this compound.Make capacitor by embodiment 1 described method, the specific energy of this capacitor can reach 4.0Wh/kg, and the 5C capacity of charging and discharging maintains 10Ah, and the 30C capacity of charging and discharging maintains 7.2mAh, and after 3000 circulations, capability retention can have 90%.(seeing table .1 for details)
Embodiment 3:
With Li
4Ti
5O
12Material is a body, places tube furnace.With toluene is carbon source, and Ar gas is as source of the gas, and the control gaseous flow blasts the toluene steam in the tube furnace, and tube furnace temperature programming therebetween is to 900 ℃ of reaction temperatures, treats that furnace temperature reaches to cause temperature requiredly, and the control furnace temperature is at reaction temperature 180min.After cooling, through grinding, promptly get required combination electrode material, the carbon covering amount of this material is 2%.Prepare capacitor anode and positive pole according to mixed slurry among the embodiment 1 and coating process, controlling the negative pole utilance equally is 60%, makes capacitor, and its barrier film and electrolyte are all with embodiment 1.Its index sees table .1 continuous item for details.Its specific energy of the system of embodiment 3 is 4.1Wh/kg, and the capacity when 30C charges and discharge is 5.9mAh, and the capacity sustainment rate after 3000 circulations is 85%.
Embodiment 4:
With Li
4Ti
5O
12Material is a body, places tube furnace.With toluene is carbon source, and Ar gas is as source of the gas.The control gaseous flow blasts the toluene steam in the tube furnace, and tube furnace is warming up to 900 ℃ of reaction temperatures therebetween, treat furnace temperature reach cause temperature required, control furnace temperature at reaction temperature 720min.After cooling, through grinding, promptly get required combination electrode material, the carbon covering amount of this material is 15%.Prepare capacitor anode and positive pole according to mixed slurry among the embodiment 1 and coating process, controlling the negative pole utilance equally is 60%, makes capacitor, and its barrier film and electrolyte are all with embodiment 1.Its index sees table .1 continuous item for details.Its specific energy only has 3.7Wh/kg, and the capacity when 30C charges and discharge is 6.7mAh, and the capacity sustainment rate after 3000 circulations is 92%.
Embodiment 5:
With Li
4Ti
5O
12Material is a body, places tube furnace.With toluene is carbon source, and Ar gas is as source of the gas, and the control gaseous flow blasts the toluene steam in the tube furnace, and tube furnace is warming up to 700 ℃ of reaction temperatures therebetween, treat furnace temperature reach cause temperature required, control furnace temperature at reaction temperature 300min.After cooling, through grinding, promptly get required combination electrode material, the carbon content of this material is 5%.Prepare capacitor anode and positive pole according to mixed slurry among the embodiment 1 and coating process, controlling the negative pole utilance equally is 60%, makes capacitor, and its barrier film and electrolyte are all with embodiment 1.Its index sees table .1 continuous item for details.Though its specific energy can reach 4.0Wh/kg, the capacity when 30C charges and discharge is 5.7mAh, and the capacity sustainment rate after 3000 circulations is 80%.
Embodiment 6:
With Li
4Ti
5O
12Material is a body, places tube furnace.With toluene is carbon source, and Ar gas is as source of the gas, and the control gaseous flow blasts the toluene steam in the tube furnace, and tube furnace is warming up to 1000 ℃ of reaction temperatures therebetween, treat furnace temperature reach cause temperature required, control furnace temperature at reaction temperature 300min.After cooling, through grinding, promptly get required lithium combination electrode material, the carbon content of this material is 5%.Prepare capacitor anode and positive pole according to mixed slurry among the embodiment 1 and coating process, controlling the negative pole utilance equally is 60%, makes capacitor, and its barrier film and electrolyte are all with embodiment 1.Its index sees table .1 continuous item for details.Find this material because preparation temperature is too high, the material oxygen loss is so all be subjected to influencing significantly on capacity and cycle performance.
Embodiment 7:
With Li
4Ti
5O
12Be bulk material, pitch is for coating carbon source.After both evenly mixed, 800 ℃ of following calcination 300min promptly got product.With this product is negative material, prepares capacitor anode and positive pole according to mixed slurry among the embodiment 1 and coating process, and controlling the negative pole utilance equally is 60%, makes capacitor, and its barrier film and electrolyte are all with embodiment 1.Its performance performance sees table .1 for details.
Table .1 contains 7# capacitor (φ 12*40L, performance comparison mm) that different lithium titanyl negative material and active carbon positive pole assemble
| Specific energy Wh/kg | Capacity mAh (5C) | Capacity mAh (30C) | Capability retention (after 3000 times) | |
| Embodiment 1 (lithium titanyl body) | 4.3 | 9.8 | 4.9 | 70％ |
| Embodiment 2 (900 ℃ of coatings of toluene, 5%) | 4.0 | 10.0 | 7.2 | 90％ |
| Embodiment 3 (900 ℃ of coatings of toluene, 2%) | 4.1 | 9.9 | 5.9 | 85％ |
| Embodiment 4 (900 ℃ of coatings of toluene, 15%) | 3.7 | 9.0 | 6.7 | 92％ |
| Embodiment 5 (700 ℃ of coatings of toluene, 5%) | 4.0 | 9.5 | 5.7 | 80％ |
| Embodiment 6 (1000 ℃ of coatings of toluene, 5%) | 4.0 | 7.6 | 4.6 | 61％ |
| Embodiment 7 (900 ℃ of liquid phases of pitch coat 5%) | 4.0 | 9.9 | 6.2 | 86％ |
Claims (5)
1, a kind of ultra-capacitor conductivity titania lithium electrode material with carbon, it is characterized in that adopting liquid phase to coat a kind of in method, gas phase cladding and the solid carbon sedimentation, bulk material is carried out carbon to coat and prepares, carbon and bulk material are the clad structure form, and described bulk material is spinel-type Li
(8x/x+4)Ti
(8/x+4)O
4, x is the mol ratio of Li/Ti, 0.5≤x≤0.8, coating layer is a carbon, coat area for the body particle surface long-pending more than 50%.
2, according to the described electrode material of claim 1, the amount that it is characterized in that coating layer is the 2-20% of electrode material total weight.
3,, it is characterized in that coating layer is agraphitic carbon or graphitized carbon according to the described electrode material of claim 1.
4, a kind of preparation method as electrode material as described in according to claim 1, it is characterized in that adopting a kind of of following method: liquid phase coats method, gas phase cladding and solid carbon sedimentation.
5, preparation method according to claim 4, the step that it is characterized in that described gas phase cladding is: bulk material is placed high temperature reaction stove, the employing inert gas is carrier gas, bring the effumability carbon source into reactor, form carbon coating layer on the bulk material surface, wherein, reaction temperature is 700-1000 ℃, and temperature retention time is 60-720 minute.
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| JP5101692B2 (en) * | 2007-06-22 | 2012-12-19 | エルジー・ケム・リミテッド | Anode material with excellent conductivity and high-power secondary battery using the same |
| KR100888685B1 (en) * | 2007-11-05 | 2009-03-13 | 주식회사 코캄 | Core-shell type anode active material for lithium secondary batteries and method of preparing for the same and lithium secondary batteries comprising the same |
| CN102332569A (en) * | 2011-03-22 | 2012-01-25 | 东莞新能源科技有限公司 | Lithium ion battery and negative electrode active material thereof |
| JP6124786B2 (en) * | 2011-03-30 | 2017-05-10 | 日本ケミコン株式会社 | Negative electrode active material, method for producing the negative electrode active material, and lithium ion secondary battery using the negative electrode active material |
| CN105206429B (en) * | 2015-10-28 | 2018-10-09 | 武汉理工大学 | A kind of fexible film electrode material and preparation method thereof |
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| CN1673180A (en) * | 2005-03-24 | 2005-09-28 | 复旦大学 | Spinel type nanometer Li-Ti oxide for negative electrode of super capacitor and its prepn process |
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