CN102623684A - Graphite-base carbonaceous anode composite material with special shell structure and preparation method for graphite-base carbonaceous anode composite material - Google Patents
Graphite-base carbonaceous anode composite material with special shell structure and preparation method for graphite-base carbonaceous anode composite material Download PDFInfo
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- CN102623684A CN102623684A CN2012101140132A CN201210114013A CN102623684A CN 102623684 A CN102623684 A CN 102623684A CN 2012101140132 A CN2012101140132 A CN 2012101140132A CN 201210114013 A CN201210114013 A CN 201210114013A CN 102623684 A CN102623684 A CN 102623684A
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Abstract
The invention belongs to the technical field of chemical power materials, and particularly relates to a graphite-base carbonaceous anode composite material with a special shell structure, a preparation method for the graphite-base carbonaceous anode composite material and application of the graphite-base carbonaceous anode composite material. The graphite-base carbonaceous anode composite material with the special shell structure is prepared by performing processes, such as micropore-forming, soaking, vapor phase deposition and pyrocarbon coating, on graphite. The special shell structure is a nuclear//shell structure of graphite// carbon nano tube or carbon fiber/metal/pyrocarbon. The graphite-base carbonaceous anode composite material has the advantage that a carbon nano tube or a carbon fiber grows in situ and is nailed between the graphite and an amorphous pyrocarbon shell; and furthermore, by using the unique pyrocarbon source, the carbon coating rate on the surface of the graphite is up to 100 percent, so that the conductivity and the stability of the shell structure of the composite material are improved, and the large-rate charge and discharge performance and the circulating performance of the material are improved. The modified graphite type material with the special shell structure has a stable structure, high capacity and high rate and circulating performance and can be used as an anode material of a small-sized lithium ion battery and a high-current charge and discharge lithium ion battery.
Description
Technical field
The invention belongs to chemical power source material technology field; Relate to a kind of phosphorus/carbon composite negative electrode material of lithium ion battery and preparation method thereof; Particularly a kind of special shell structurre natural graphite base negative material is specially the preparation and the application thereof of carbon composite of the nuclear // shell structure of graphite // CNT or carbon fiber/metal/RESEARCH OF PYROCARBON.
Background technology
At present, along with global non-renewable energy resources resource is petered out, energy supply and demand contradiction is becoming increasingly acute, and the countries in the world ubiquity multi-form energy crisis, thereby the development and use of new forms of energy are become one of focus of people's concern.Simultaneously, problems such as environmental pollution that causes in the particularly exploitation of fossil energy resources process of the energy and ecological disruption are outstanding day by day, and the Global climate change that the ability source emission causes has proposed challenge to human existence and economic development mode.For this reason, encouragement taps a new source of energy becomes the energy strategy emphasis of numerous countries with new-energy automobile.Electrokinetic cell is new-energy automobile " heart ", and battery material is the core of supporting motive force battery.Therefore, the key technology of new-energy automobile still is the exploitation of new energy materials.In all kinds of electrokinetic cells, power lithium-ion battery is to become the most potential new-energy automobile power source with its excellent performance and resource.Active development cheapness and high performance power lithium ion battery electrode material have important social and economic significance.Negative material is the critical material of power lithium-ion battery.Seek new technology, produce high power capacity, high power, long circulation life and negative material is of far-reaching significance cheaply.
What present commercial lithium ion battery negative material mainly adopted is native graphite and Delanium.Wherein, the Delanium production cost is high, capacity is on the low side.The big high rate performance of native graphite is not good enough, but aboundresources, cheap, degree of crystallinity is high, discharge platform is more steady after deep processing, structural stability is good, can satisfy its requirement.Present stage, generally improve its capacity and high rate performance through the graphite-like negative material being carried out surface oxidation, carbon coating and modified methods such as surface deposition layer of metal or metal oxide.Wherein, graphite type material is carried out the reversible capacity that surface oxidation treatment has improved graphite to a certain extent, but the high-rate performance of graphite after the modification is not done further research; Traditional organic resin class or the fragmentation of polymer pyrolysis carbon source cladded type graphite-base composite material after coating are difficult to prepare the intact core-shell material of coating, thereby cause the material surface stability not good; And because the volumetric expansion effect of metal alloy, behind graphite surface plated metal or metal oxide, the charge/discharge capacity under the big electric current is still lower.This project is through design and prepare a kind of special shell structurre; The nuclear of graphite // CNT or carbon fiber/metal/RESEARCH OF PYROCARBON // shell carbon compound cathode materials; Through the multicomponent coordinating effect; Have complementary advantages, can access power lithium-ion battery with high structural stability and high power modified graphite base carbon anode material, thereby actively push forward further developing of new-energy automobile industry.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of special shell structurre graphite-based carbon composite material.Graphite through processes such as microporeization, dipping, vapour deposition and RESEARCH OF PYROCARBON coatings, is made the graphite-based carbon composite material with special shell structurre, be specially the nuclear // shell structure of graphite // CNT or carbon fiber/metal/RESEARCH OF PYROCARBON.Advantage applies of the present invention exists: through growth in situ CNT or carbon fiber; Be pinned between graphite and amorphous RESEARCH OF PYROCARBON shell; Utilize its good electric conductivity and mechanical performance; Improve composite material core-shell structural conductive property and stability, and then improve material high rate charge-discharge performance and cycle performance; Simultaneously, utilize unique pyrolysis carbon source, make the graphite surface clad ratio reach 100%.The modified graphite class material of this special shell structurre has high structural stability, high electrochemistry capacitance, high magnification and high cycle performance, can satisfy the application of small lithium ion secondary batteries and high current charge-discharge lithium ion power cell cathode.
The invention provides the method that a kind of preparation has the silicon/carbon/graphite in lithium ion batteries base carbon anode material of special shell structurre, material has the nuclear // shell structure of graphite // CNT or carbon fiber/metal/RESEARCH OF PYROCARBON.
This method comprises that the following step gathers:
(1) microporeization: graphite slowly added in the liquid solution fully stirs, through liquid-solid reaction, make graphite surface form uniform micro-nano micropore after, washing, Separation of Solid and Liquid obtain micropore fossil China ink.
(2) dipping: will be immersed in the salting liquid of metallic catalyst through the graphite after the surface microporeization early stage; Fully stir and infiltration; Through strictness control concentration of salt solution, dipping temperature and the time; The metallic catalyst ion is fully got in the middle of the nanometer micropore of graphite, and it is dry to centrifugalize liquid-solid back, obtains the modified graphite of metallic catalyst ion dipping.
(3) vapour deposition: carry out the hydrogen reducing reaction earlier, then through the micropore graphite surface growth in situ CNT or the carbon fiber of vapour deposition process behind dipping.
(4) surface coats: the graphite of vapour deposition modification is immersed in the aqueous solution or organic solution of organic carbon source; The modified graphite that stir, evaporating solvent obtains coated with uniform one deck organic carbon evenly coats the amorphous carbon layer that one deck is obtained by the organic carbon source pyrolysis through oven dry, high temperature pyrolysis at graphite surface.
The used graphite of the present invention comprises one or more in natural flake graphite, micro crystal graphite, Delanium and the high temperature graphitization material with carbon element (MCMB and CMS).
The used liquid solution of the present invention is an oxidizing solution, comprises in sulfuric acid and sulfate, persulfate, hydrogen peroxide solution, nitric acid and the nitrate one or more.
In the soluble-salt solution that the used metallic catalyst salting liquid of the present invention is Fe, Co, Ni one or more.
The needed carbon-source gas of CNT or carbon fibre growth is one or more in the hydrocarbons such as methane, ethane, propane, ethene, propylene, acetylene, natural gas, oil liquefied gas among the present invention.
It is glucose, sucrose, resinae polymer, pitch, polyvinyl chloride, polyacrylonitrile that the present invention selects organic carbon source for use; Selecting solvent for use is in water, ethanol, acetone, carbon disulfide, the oxolane one or more.
The special shell structurre graphite-based carbon anode material of the present invention's preparation has good electrochemistry capacitance and high rate charge-discharge performance; Under the 0.2C multiplying power, discharge and recharge; Reversible capacity is higher than 360 mAh/g, and coulombic efficiency is higher than 93% first, and circulating, capability retention is higher than 92% after 100 times; Under 1C and 3C multiplying power, reversible capacity is higher than 340 and 320 mAh/g respectively, and coulombic efficiency is higher than 85% first, circulates that capability retention is higher than 85% after 100 times, is the high performance lithium ionic cell cathode material that application prospect is arranged very much.
Embodiment
In the method for the special shell structurre graphite-based carbon composite negative pole material that the present invention relates to, step (1) relates to the micropore metallization processes of graphite surface, and this step is that follow-up impregnation technology provides sufficient uniform micro-nano hole and passage.Used graphite comprises one or more in natural flake graphite, micro crystal graphite, Delanium and the high temperature graphitization material with carbon element (MCMB and CMS) in this step; The weight ratio of material with carbon element and liquid solution is 0.2-8; Liquid solution is an oxidizing solution, comprises in sulfuric acid and sulfate, persulfate, hydrogen peroxide solution, nitric acid and the nitrate one or more, and solution concentration is 0.05-3mol/L.This step reaction temperature and time is respectively 0-80 ℃, 0.5-10hr.Step (2) relates to micropore fossil China ink impregnation technology, and the metal ion of dipping infiltration into microporous is the catalyst precursor in the follow-up vapour deposition process in this step.In the soluble-salt that used metallic catalyst salting liquid is Fe, Co, Ni in this step one or more, concentration are 0.05-1mol/L; Dipping temperature and time are respectively 0-80 ℃, 0.5-10hr.Step (3) relates to gas-phase deposition, and micropore graphite surface growth in situ CNT or carbon fiber behind dipping utilize its pinning effect, and nano-sized carbon is taken root in the graphite surface micropore evenly, securely.At first utilize hydrogen reducing reaction to obtain among metallic catalyst Fe, Co, the Ni one or more in this step, its flow velocity is the 1-1000 ml/min, and the time is 0.5-5 hour; The needed carbon-source gas of CNT or carbon fibre growth is one or more in the hydrocarbons such as methane, ethane, propane, ethene, propylene, acetylene, natural gas, oil liquefied gas, and its flow velocity is the 1-1000 ml/min; Depositing temperature is 500-1200 ℃, and the time is 0.1-5hr; Diluent gas is all high pure nitrogen.Step (4) relates to surface cladding tech, and the graphite surface behind CNT or carbon fiber pinning evenly coats one deck pyrolysis amorphous carbon again.Selecting organic carbon source in this step for use is glucose, sucrose, resinae polymer, pitch, polyvinyl chloride, polyacrylonitrile, and mass percent is 3-15%; Selecting solvent for use is in water, ethanol, acetone, carbon disulfide, the oxolane one or more; Soaking and stirring 0.5-6 hour, evaporate to dryness temperature are 50-120 ℃, and pyrolysis temperature is 700-1200 ℃, and the time is 2-10hr.
Embodiment 1:
Natural flake graphite is slowly added in the hydrogen peroxide solution that 200ml concentration is 0.5M, and the weight ratio of graphite and liquid solution is 4, stirs 5 hours at 40 ℃; Behind Separation of Solid and Liquid, cyclic washing, be in the 0.6M iron nitrate solution in concentration, 40 ℃ flooded 5 hours; The product that will carry out again after Separation of Solid and Liquid, the vacuumize places tube furnace, and the hydrogen of earlier logical 600 ml/min 3 hours is then in the acetylene air-flow of 600 ml/min; 800 ℃ of deposit are 3 hours; Constant temperature growth in situ CNT or carbon fiber, it is in 8% the aqueous sucrose solution that the graphite of vapour deposition nano-sized carbon is immersed in mass percent, stirs after 3 hours; Stir evaporate to dryness at 70 ℃, promptly get core/shell structure carbon anode material after 5 hours at 800 ℃ of high temperature pyrolysis.
With the preparation material as negative pole, the lithium sheet is to electrode, U.S. Celgard 2400 is a barrier film, 1.0 mol/L LiPF6/EC+DMC [V (EC): V (DMC)=1:1] are electrolyte, in being full of the stainless steel glove box of argon gas, are assembled into button cell.On Land-BTL10 (indigo plant) full-automatic battery controlled testing instrument, carry out the constant current constant voltage charge-discharge test, discharge-rate is respectively 0.1-3C, and the charging/discharging voltage scope is 0.005-3 V.Under the 0.2C multiplying power, discharge and recharge, reversible capacity is 367 mAh/g, and coulombic efficiency is 92% first, and capability retention 94% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is higher than 350 and 336 mAh/g respectively, and coulombic efficiency is higher than 89% first, and circulating, capability retention is higher than 86% after 100 times.
Embodiment 2:
Natural micro crystal graphite is slowly added in the ammonium persulfate solution that 200ml concentration is 0.4M, and the weight ratio of graphite and liquid solution is 6, stirs 4 hours at 40 ℃; Behind Separation of Solid and Liquid, cyclic washing, be in the 0.4M cobalt nitrate solution in concentration, 40 ℃ flooded 5 hours; The product that will carry out again after Separation of Solid and Liquid, the vacuumize places tube furnace, and the hydrogen of earlier logical 600 ml/min 3 hours is then in the liquefied petroleum entraining air stream of 600 ml/min; 750 ℃ of deposit are 3 hours; Constant temperature growth in situ CNT or carbon fiber, it is in 8% the phenolic resins organic solution that the graphite of vapour deposition nano-sized carbon is immersed in mass percent, stirs after 3 hours; Stir evaporate to dryness at 70 ℃, promptly get core/shell structure carbon anode material after 5 hours at 800 ℃ of high temperature pyrolysis.
Obtain with the test of identical electrochemical method, under the 0.2C multiplying power, discharge and recharge, reversible capacity is 354 mAh/g, and coulombic efficiency is 91% first, and capability retention 93% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is higher than 340 and 323 mAh/g respectively, and coulombic efficiency is higher than 85% first, and circulating, capability retention is higher than 84% after 100 times.
Embodiment 3:
MCMB is slowly added in the ammonium persulfate solution that 200ml concentration is 0.5M, and the weight ratio of graphite and liquid solution is 3, stirs 5 hours at 40 ℃; Behind Separation of Solid and Liquid, cyclic washing, be in the 0.4M nickel nitrate solution in concentration, 40 ℃ flooded 5 hours; The product that will carry out again after Separation of Solid and Liquid, the vacuumize places tube furnace, and the hydrogen of earlier logical 600 ml/min 3 hours is then in the methane gas stream of 600 ml/min; 750 ℃ of deposit 3 hours; Constant temperature growth in situ CNT or carbon fiber, it is in 10% the D/W that the graphite of vapour deposition nano-sized carbon is immersed in mass percent, stirs after 3 hours; Stir evaporate to dryness at 70 ℃, promptly get core/shell structure carbon anode material after 5 hours at 800 ℃ of high temperature pyrolysis.
Obtain with the test of identical electrochemical method, under the 0.2C multiplying power, discharge and recharge, reversible capacity is 328 mAh/g, and coulombic efficiency is 95% first, and capability retention 96% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is higher than 322 and 313 mAh/g respectively, and coulombic efficiency is higher than 92% first, and circulating, capability retention is higher than 93% after 100 times.
Embodiment 4:
Natural flake graphite is slowly added in the potassium peroxydisulfate and hydrogen peroxide solution that 200ml concentration is 0.5M, and the weight ratio of graphite and liquid solution is 2, stirs 5 hours at 50 ℃; Behind Separation of Solid and Liquid, cyclic washing, be in the 0.8M nickel nitrate solution in concentration, 50 ℃ flooded 5 hours; The product that will carry out again after Separation of Solid and Liquid, the vacuumize places tube furnace, and the hydrogen of earlier logical 900 ml/min 2 hours is then in the acetylene air-flow of 900 ml/min; 750 ℃ of deposit are 3 hours; Constant temperature growth in situ CNT or carbon fiber are immersed in the graphite of vapour deposition nano-sized carbon in the ethanol and water mixed solution that mass percent is 12% glucose, stir after 3 hours; At 60 ℃ of vacuum stirring evaporates to dryness, promptly get core/shell structure carbon anode material after 10 hours at 750 ℃ of high temperature pyrolysis.
Obtain with the test of identical electrochemical method, under the 0.2C multiplying power, discharge and recharge, reversible capacity is 366 mAh/g, and coulombic efficiency is 95% first, and capability retention 95% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is higher than 358 and 349 mAh/g respectively, and coulombic efficiency is higher than 90% first, and circulating, capability retention is higher than 95% after 100 times.
Embodiment 5:
Natural flake graphite is slowly added in the cerous sulfate solution that 200ml concentration is 1M, and the weight ratio of graphite and liquid solution is 2, stirs 3 hours at 50 ℃; Behind Separation of Solid and Liquid, cyclic washing, be in the 0.5M nickel nitrate solution in concentration, 50 ℃ flooded 5 hours; The product that will carry out again after Separation of Solid and Liquid, the vacuumize places tube furnace, and the hydrogen of earlier logical 800 ml/min 3 hours is then in the acetylene air-flow of 800 ml/min; 760 ℃ of deposit are 5 hours; Constant temperature growth in situ CNT or carbon fiber, it is in 10% the polyvinyl chloride organic solution that the graphite of vapour deposition nano-sized carbon is immersed in mass percent, stirs after 5 hours; Stir evaporate to dryness at 70 ℃, promptly get core/shell structure carbon anode material after 6 hours at 760 ℃ of high temperature pyrolysis.
Obtain with the test of identical electrochemical method, under the 0.2C multiplying power, discharge and recharge, reversible capacity is 356 mAh/g, and coulombic efficiency is 95% first, and capability retention 96% after 100 times circulates; Under 1C and 3C multiplying power, reversible capacity is higher than 348 and 332 mAh/g respectively, and coulombic efficiency is higher than 86% first, and circulating, capability retention is higher than 92% after 100 times.
Claims (6)
1. the preparation method of the graphite-based carbon anode material of a special shell structurre; It is characterized in that: through growth in situ CNT or carbon fiber; Be pinned between graphite and the amorphous carbon; Form high conductivity and high structural stability, have the carbon anode material of the nuclear // shell structure of graphite // CNT or carbon fiber/metal/RESEARCH OF PYROCARBON.This preparation method's concrete steps are:
(1) microporeization: graphite is slowly added in the liquid solution that concentration is 0.05-3M, and the weight ratio of graphite and liquid solution is 0.2-8,0-80 ℃ stir 0.5-10 hour after, Separation of Solid and Liquid, cyclic washing.
(2) dipping: it is in the 0.05-1M salting liquid that surface micropore fossil China ink is immersed in concentration, and dipping temperature is 0-80 ℃, and the time is 0.5-10 hour, through Separation of Solid and Liquid, vacuumize.
(3) vapour deposition: hydrogen 0.5-5 hour of 1-1000 ml/min led in elder generation; Carry out reduction reaction; Be in the carbon-source gas of 1-1000 ml/min at flow velocity then; 500-1200 ℃ of deposit is 0.1-5 hour, constant temperature growth in situ CNT or carbon fiber, and diluent gas is all high pure nitrogen.
(4) surface coats: the graphite of vapour deposition nano-sized carbon is immersed in the organic carbon source solution that mass percent is 3-15%; Stirred 0.5-6 hour; Again after evaporating solvent is stirred in 50-120 ℃ of continuation; At 700-1200 ℃ of high temperature pyrolysis 2-10 hour, promptly get the carbon anode material of nuclear // shell structure with graphite // CNT or carbon fiber/metal/RESEARCH OF PYROCARBON.
2. according to the described preparation method of claim 1, the said graphite of step (1) comprises one or more in natural flake graphite, micro crystal graphite, Delanium and the high temperature graphitization material with carbon element (MCMB and CMS).
3. according to the described preparation method of claim 1, the said liquid solution of step (1) is an oxidizing solution, comprises in sulfuric acid and sulfate, persulfate, hydrogen peroxide solution, nitric acid and the nitrate one or more.
4. according to the described preparation method of claim 1, the said salting liquid of step (2) is the metallic catalyst salting liquid, comprises in the soluble-salt of Fe, Co, Ni one or more.
5. according to the described preparation method of claim 1, the said carbon-source gas of step (3) is one or more in the hydrocarbons such as methane, ethane, propane, ethene, propylene, acetylene, natural gas, oil liquefied gas.
6. according to the described preparation method of claim 1, the said organic carbon source of step (4) is glucose, sucrose, resinae polymer, pitch, polyvinyl chloride, polyacrylonitrile; Selecting solvent for use is in water, ethanol, acetone, carbon disulfide, the oxolane one or more.
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| CN103199254A (en) * | 2013-04-03 | 2013-07-10 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite negative material of lithium-ion battery and preparation method of negative material |
| CN105070916A (en) * | 2015-09-08 | 2015-11-18 | 湖南星城石墨科技股份有限公司 | Preparation method of highly compacted carbon-coated natural graphite material |
| CN106276859A (en) * | 2016-08-15 | 2017-01-04 | 天津大学 | A kind of preparation method of the CNT microsphere being coated with carbon film |
| WO2020199354A1 (en) * | 2019-04-04 | 2020-10-08 | 碳翁(北京)科技有限公司 | High-temperature-resistant electrothermal fiber and application thereof |
| CN113764644A (en) * | 2021-09-15 | 2021-12-07 | 河北坤天新能源科技有限公司 | Quick-filling composite graphite material and preparation method thereof |
| CN111430691B (en) * | 2020-03-31 | 2021-12-07 | 北京卫蓝新能源科技有限公司 | Silicon-based negative electrode material of lithium ion battery and preparation method thereof |
| CN113851614A (en) * | 2020-06-28 | 2021-12-28 | 上海昱瓴新能源科技有限公司 | Low-temperature quick-charging artificial graphite cathode material, preparation method thereof and low-temperature quick-charging battery |
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| CN113851614A (en) * | 2020-06-28 | 2021-12-28 | 上海昱瓴新能源科技有限公司 | Low-temperature quick-charging artificial graphite cathode material, preparation method thereof and low-temperature quick-charging battery |
| CN113903913A (en) * | 2021-08-24 | 2022-01-07 | 中南大学 | Graphitized carbon nanofiber/carbon nanofiber @ graphite composite powder material and preparation method and application thereof |
| CN113764644A (en) * | 2021-09-15 | 2021-12-07 | 河北坤天新能源科技有限公司 | Quick-filling composite graphite material and preparation method thereof |
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Application publication date: 20120801 |