CN109859957A - A kind of carbon and titanium niobium oxide composite negative pole material and its preparation and application - Google Patents
A kind of carbon and titanium niobium oxide composite negative pole material and its preparation and application Download PDFInfo
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- CN109859957A CN109859957A CN201711238339.5A CN201711238339A CN109859957A CN 109859957 A CN109859957 A CN 109859957A CN 201711238339 A CN201711238339 A CN 201711238339A CN 109859957 A CN109859957 A CN 109859957A
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- niobium oxide
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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 a kind of carbon and titanium niobium oxide composite negative pole material and its preparations and application, and mass content 90~95% of the titanium niobium oxide in composite negative pole material, the mass content of carbon in the composite is 5-10%.Compared with prior art, the present invention is using ultracentrifugation effect and sol-gal process and introduces with highly conductive carbon material, the highly conductive titanium niobium oxide composite material with nano-scale is prepared, the nanochannel of particle increases the effective affecting acreage of electrode and the access way of ion；The introducing of carbon material can form effective conductive network in the composite, improve the electric conductivity of material, while carbon material plays the role of support and cladding to titanium niobium oxide, improve its cycle performance while improving titanium niobium oxide high rate performance.
Description
Technical field
The present invention relates to technical field of lithium ion, in particular to a kind of lithium ion super capacitor negative electrode material.
Background technique
Electric chemical super capacitor is a kind of energy storage device to be worked based on electric double layer or pseudo capacitance mechanism, due to
Have many advantages, such as that charge/discharge speed is fast, power density is high, have extended cycle life, operating temperature range is wide and receives significant attention.With
Lithium ion battery is compared, and electrochemical capacitor energy density is relatively low, but it has extended cycle life, and is widely used in electric car
The fields such as starter, the pulse power and mobile backup power source.With hybrid-electric car and its to high power density and energy
The demand of metric density, lithium ion super capacitor obtain more and more extensive concern as a kind of novel energy storage device.But
Since lithium ion super capacitor uses the electrode of lithium ion battery and supercapacitor to have with double grading simultaneously
Advantage bigger than conventional capacitor energy density, bigger than lithium ion battery power density.Therefore, lithium ion super capacitor is expected to
For the powerful electronics field of the energy types such as electric car, space flight, military affairs.
The negative electrode material of current commercialized lithium ion super capacitor is mainly hard carbon, but its charge-discharge velocity is slow,
Have been unable to meet the demand of some users；
Lithium titanate material is in charge and discharge process, and with the insertion and abjection of lithium ion, lithium titanate hardly happens volume
Variation, therefore it is referred to as " zero strain material "；Since (1.55V (vs.Li/Li+) is higher than most of organic baths to its embedding lithium platform
Reduction potential, therefore can effectively avoid SEI formation and Li dendrite caused by safety problem.However, lithium titanate is lower
Capacity leads to its application of the energy density lower limit of full battery.
Titanium niobium oxide high rate charge-discharge performance with higher, high capacity and highly stable cycle performance and it is standby
It is concerned.But titanium niobium oxide conductivity and lithium ion diffusivity need to be improved.
Summary of the invention
The invention solves the problems of the conductive difference of the titanium niobium oxide negative electrode material of existing method preparation, and provide a kind of benefit
Carbon/titanium niobium oxide composite material method is prepared with ultracentrifugation effect and sol-gal process.
To achieve the above object, the specific technical solution of the present invention is as follows,
A method of carbon/titanium niobium oxide composite material, feature are prepared using ultracentrifugation effect and sol-gal process
Be: titanium niobium oxide is in the mass content 90~95% on composite negative pole material, the mass content of carbon in the composite
5-10%.
The best in quality content that the present invention obtains each component in carbon/titanium niobium oxide composite material is: titanium niobium oxide is
95%, CNT are 5%.
Carbon/titanium niobium oxide composite material and preparation method thereof sequentially includes the following steps:
(1) titanium niobium oxide TiNb is pressed2O7Stoichiometric ratio, weigh titanium source and niobium source respectively and be dissolved in organic
In solvent, wherein niobium source is the mixing of one or both of niobium pentaoxide and niobium hydroxide；Titanium source is butyl titanate, metatitanic acid
The mixing of one or more of butyl ester or tetra-n-butyl titanate；
(2) carbon nanotube, graphite and carbon source are dissolved in water or organic solvent, 1~3h of ultrasound
(3) titanium source and niobium source solution that step (1) obtains are added separately to solution in step (2) and are stirred when being added
It mixes, above-mentioned mixed solution is added in centrifuge tube, ultracentrifugation is carried out to it, centrifugal speed is 60000~65000r/
Min, time 3-15min.Product is heated at 50-100 DEG C after centrifugation, it is compound to obtain titanium niobium oxide by time 15-25h
Material precursor；
(5) titanium niobium oxide composite material precursor is placed in tube furnace, under reducing atmosphere, temperature is 600~900
8~12h is reacted under conditions of DEG C, obtains carbon/titanium niobium oxide composite material；
Organic solvent is methanol, ethyl alcohol, isopropanol, ethylene glycol one or two or more kinds.
Mass concentration of the lithium source in solvent in step (1) is 10-80g/L, conductive carbon and oxidation stone in step (2)
Black alkene gross mass accounts for the 1-5g/L of solvent volume.
In step (2), ultrasonic power is 200~700W, and the speed stirred in step (3) is 200~800rpm.
Reducing atmosphere described in step (3) is H2With the gaseous mixture of inert gas, the wherein volume of the total gaseous mixture of hydrogen Zhan
Concentration is 1%~10%, and inert gas is argon gas, helium or nitrogen.
The carbon/titanium niobium oxide anode material is used for the cathode material of lithium ion super capacitor as active constituent
Material.
Beneficial outcomes of the invention:
Lithium titanate with nano-scale is prepared using ultracentrifugation effect and sol-gal process, ultracentrifugation effect makes metatitanic acid
Lithium particle height is dispersed in conductive carbon, so that composite material has high conductivity.The nanochannel of lithium titanate particle increases
The effective affecting acreage of electrode and the access way of ion；Carbon material plays the role of support and cladding to titanium niobium oxide simultaneously,
Improve its cycle performance while improving titanium niobium oxide high rate performance.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it
Between any combination.
Embodiment 1:
The present embodiment lithium ion super capacitor is sequentially included the following steps: with carbon/titanium niobium oxide anode material
(1) titanium niobium oxide TiNb is pressed2O7Stoichiometric ratio, weigh 8.5mL butyl titanate and 13.3g five respectively and aoxidize
Two niobium dispersing and dissolvings are in 100mL dehydrated alcohol；
(2) it weighs 0.2g CNT and places it in the beaker equipped with 200mL ethyl alcohol, after the power ultrasound 1h of 600W,
The alcohol dispersion liquid of butyl titanate and niobium pentaoxide in step (1) is slowly added into the ethanol solution of CNT；
(3) above-mentioned mixed solution is added in centrifuge tube, ultracentrifugation, centrifugal speed 61000r/ is carried out to it
Min, time 8min.Product is heated at 70 DEG C after centrifugation, time 20h obtains titanium niobium oxide composite material precursor；
By it in 3%H2Under the reducing atmosphere of/Ar, 8h is reacted under the conditions of 700 DEG C of temperature, obtains CNT/ titanium niobium oxide composite wood
Material, titanium niobium oxide is in the mass content 95% on composite negative pole material.
Raw materials used the present embodiment is commercial product.
Performance test:
1) in the composite material CNT/ titanium niobium oxide of preparation: the ratio of Super P:PVDF=8:1:1 mixes, and uses N-
Methyl pyrrolidone is solvent, and with the speed of 400rpm, magnetic agitation 4h obtains electrode slurry, is applied on aluminium foil, makes to carry on a shoulder pole
Amount control is in~3.5mg/cm2, 100 DEG C at a temperature of, be dried in vacuo 12h, being then washed into long diameter with sheet-punching machine is 14mm
Electrode slice.
Electrolyte used is methyl ethyl carbonate rouge (EMC), ethylene carbonate (EC), propene carbonate (PC) and dimethyl carbon
One of acid esters (DMC) or in which several mixed liquors, electrolyte used in the present embodiment are the lithium ion battery batteries of business
Liquid is solved, wherein lithium salts is lithium hexafluoro phosphate, and solvent is the mixed liquor of EC, DEC and DMC that volume ratio is 1:1:1.
Embodiment 2:
Carbon/titanium niobium oxide composite material and battery are prepared using method same as Example 1, the difference is that CNT
Content, mass percentage are 10%.
Embodiment 3: preparing carbon/titanium niobium oxide composite material and battery using method same as Example 1, different
It is carbon material is graphene, mass percentage is 5%.
Comparative example 1: cathode assembled battery as active material and is prepared using pure titanium niobium oxide, pure titanium niobium oxide system
Preparation Method and battery assembly method are same as Example 1.
Claims (9)
1. a kind of carbon and titanium niobium oxide composite negative pole material, it is characterised in that: titanium niobium oxide is in composite negative pole material
Mass content 90~95%, the mass content of carbon in the composite is 5-10%.
2. composite negative pole material according to claim 1, it is characterised in that: wherein carbon include graphene, it is carbon nanotube, porous
One or more of carbon, porous carbon are wrapped in outside titanium niobium oxide, are enclosed with the titanium niobium oxide or titanium of porous carbon
Niobium oxide is carried in graphene or carbon nanotube.
3. composite negative pole material according to claim 1, it is characterised in that: titanium niobium oxide is TiNb2O7。
4. a kind of preparation method of composite negative pole material described in claim 1-3, which is characterized in that ultracentrifugation effect and colloidal sol
Gel method prepares carbon/titanium niobium oxide composite material and sequentially includes the following steps:
(1) titanium niobium oxide TiNb is pressed2O7Stoichiometric ratio, weigh titanium source and niobium source respectively and be dissolved in organic solvent
In, wherein niobium source is the mixing of one or both of niobium pentaoxide and niobium hydroxide；Titanium source is butyl titanate, butyl titanate
Or one or more of tetra-n-butyl titanate mixing；
(2) water is dispersed by one of carbon source of carbon nanotube, graphite and porous carbon or two kinds or more carbonaceous material and/or have
In solvent, 1~3h of ultrasound；The carbon source of porous carbon is sucrose, glucose, one or more kinds of in citric acid；
(3) titanium source and niobium source solution that step (1) obtains are added separately to solution in step (2) and stirred while adding,
Above-mentioned mixed solution is added in centrifuge tube, ultracentrifugation is carried out to it, centrifugal speed is 60000~65000r/min, when
Between be 3-15min；Product is heated at 50-100 DEG C after centrifugation, time 15-25h, before obtaining titanium niobium oxide composite material
Body；
(5) titanium niobium oxide composite material precursor is placed in tube furnace, under reducing atmosphere, temperature is 600~900 DEG C
Under the conditions of react 8~12h, obtain carbon/titanium niobium oxide composite material.
5. according to claim 4 prepare carbon/titanium niobium oxide composite material using ultracentrifugation effect and sol-gal process
Method, it is characterised in that: organic solvent is that methanol, ethyl alcohol, isopropanol, ethylene glycol are one or two or more kinds of.
6. according to claim 4 prepare carbon/titanium niobium oxide composite material using ultracentrifugation effect and sol-gal process
Method, it is characterised in that: the mass concentration of niobium in step (1) in solvent is 10-80g/L, carbon containing in step (2)
The mass concentration of substance is 1-5g/L.
7. according to claim 4 prepare carbon/titanium niobium oxide composite material using ultracentrifugation effect and sol-gal process
Method, it is characterised in that: in step (2), ultrasonic power be 200~700W.
8. according to claim 4 prepare carbon/titanium niobium oxide composite material using ultracentrifugation effect and sol-gal process
Method, it is characterised in that: reducing atmosphere described in step (3) be H2With the gaseous mixture of inert atmosphere gases, wherein hydrogen is accounted for
The volumetric concentration of total gaseous mixture is 1%~10%, inert atmosphere gases be one or both of argon gas, helium or nitrogen with
On.
9. a kind of application of carbon described in claim 1-3/titanium niobium oxide composite material, it is characterised in that: the carbon/titanium niobium oxygen
The negative electrode material of compound composite material being used for as active constituent in lithium ion super capacitor.
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| CN110400923A (en) * | 2019-07-29 | 2019-11-01 | 珠海格力电器股份有限公司 | Cell negative electrode material, negative electrode material slurry, cathode pole piece and electrochemical cell |
| CN111628176A (en) * | 2020-06-17 | 2020-09-04 | 苏州盟维动力科技有限公司 | Multi-component three-dimensional conductive carbon network, self-supporting composite electrode, and preparation methods and applications thereof |
| CN112447940A (en) * | 2019-09-04 | 2021-03-05 | 通用汽车环球科技运作有限责任公司 | Titanium niobium oxide and titanium oxide composite anode material |
| CN112736250A (en) * | 2020-12-30 | 2021-04-30 | 安徽科达铂锐能源科技有限公司 | Carbon-coated niobium-doped modified titanium niobate material and preparation method thereof |
| CN113233504A (en) * | 2021-04-29 | 2021-08-10 | 武汉理工大学 | Preparation method and application of high-conductivity titanium niobate negative electrode material |
| CN114300665A (en) * | 2021-12-30 | 2022-04-08 | 华南师范大学 | Niobium-based metal oxide mesoporous carbon sphere composite material and sodium ion battery anode material containing same |
| WO2022260318A1 (en) * | 2021-06-11 | 2022-12-15 | 한양대학교에리카산학협력단 | Anode active material comprising transition metal oxide, anode using same, and preparation method for anode active material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110400923A (en) * | 2019-07-29 | 2019-11-01 | 珠海格力电器股份有限公司 | Cell negative electrode material, negative electrode material slurry, cathode pole piece and electrochemical cell |
| CN112447940A (en) * | 2019-09-04 | 2021-03-05 | 通用汽车环球科技运作有限责任公司 | Titanium niobium oxide and titanium oxide composite anode material |
| CN111628176A (en) * | 2020-06-17 | 2020-09-04 | 苏州盟维动力科技有限公司 | Multi-component three-dimensional conductive carbon network, self-supporting composite electrode, and preparation methods and applications thereof |
| CN111628176B (en) * | 2020-06-17 | 2022-01-28 | 苏州盟维动力科技有限公司 | Multi-component three-dimensional conductive carbon network, self-supporting composite electrode, and preparation methods and applications thereof |
| CN112736250A (en) * | 2020-12-30 | 2021-04-30 | 安徽科达铂锐能源科技有限公司 | Carbon-coated niobium-doped modified titanium niobate material and preparation method thereof |
| CN113233504A (en) * | 2021-04-29 | 2021-08-10 | 武汉理工大学 | Preparation method and application of high-conductivity titanium niobate negative electrode material |
| WO2022260318A1 (en) * | 2021-06-11 | 2022-12-15 | 한양대학교에리카산학협력단 | Anode active material comprising transition metal oxide, anode using same, and preparation method for anode active material |
| KR20220166968A (en) * | 2021-06-11 | 2022-12-20 | 한양대학교 에리카산학협력단 | anode active material containing transition metal oxide, anode electrode using the same, and method for fabricating the same |
| KR102512366B1 (en) * | 2021-06-11 | 2023-03-20 | 한양대학교 에리카산학협력단 | anode active material containing transition metal oxide, anode electrode using the same, and method for fabricating the same |
| CN114300665A (en) * | 2021-12-30 | 2022-04-08 | 华南师范大学 | Niobium-based metal oxide mesoporous carbon sphere composite material and sodium ion battery anode material containing same |
| CN114300665B (en) * | 2021-12-30 | 2024-04-09 | 华南师范大学 | Niobium-based metal oxide mesoporous carbon sphere composite material and sodium ion battery anode material containing same |
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