CN100413127C - Carbonaceous lithium ion battery negative electrode material with nuclear shell structure and producing method thereof - Google Patents
Carbonaceous lithium ion battery negative electrode material with nuclear shell structure and producing method thereof Download PDFInfo
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- CN100413127C CN100413127C CNB2006100116111A CN200610011611A CN100413127C CN 100413127 C CN100413127 C CN 100413127C CN B2006100116111 A CNB2006100116111 A CN B2006100116111A CN 200610011611 A CN200610011611 A CN 200610011611A CN 100413127 C CN100413127 C CN 100413127C
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Abstract
The present invention relates to negative pole materials of a carbonaceous lithium ion battery with a core shell structure and a preparation method of the negative pole materials of the carbonaceous lithium ion battery, which belongs to the technical field of carbon materials and a chemical power source. The negative pole materials are composed of a core part and a shell part, wherein the core part is provided with graphite obtained after a compound among graphite layers is shed and inserted, and the shell part is provided with amorphous carbon obtained through pyrolyzing organic substances. The present invention has the preparation method that compound micro powder with 5 to 50 mu m granularity among the graphite layers is firstly prepared, is slowly shed and inserted after the compound micro powder is heated for 12 to 72 hours at the temperature of 100 to 350 DEG C, is coated with the organic substances at the surface of the graphite after shedding and insertion, and is carbonized in the range of 700 to 1100 DEG C. The present invention uses the amorphous carbon with a stable structure for coating and forming a shell to reduce an irreversible quantity for the first time, inner cores of compound granules among the graphite layers are slowly shed and inserted to form gaps from a nanon order to a micron order, and rise and shrinkage space is reserved so as to improve cycle performance. The provided negative pole materials of a carbonaceous lithium ion battery with a core shell structure have the advantages of high capacity, low irreversible capacity for the first time, high cycle efficiency and long cycle life.
Description
Technical field
The present invention relates to carbonaceous lithium ion battery negative electrode material of a kind of nucleocapsid structure and preparation method thereof, belong to material with carbon element and technical field of chemical power.
Background technology
Lithium ion battery has been showed wide application prospect and potential great economic benefit with advantages such as high-energy-density, long circulation life, environmental protections, and in the evolution of lithium ion battery, the research and development of negative material occupies critical role always.Carbon material (comprising graphite, MCMB, organic carbon thing, petroleum coke etc.) becomes with its height ratio capacity, low electrode current potential, high cycle efficieny and long circulation life and uses and study negative material the most widely.
Graphite comprises natural micro crystal graphite, natural flake graphite, electrographite etc.Still there are some problems in undressed graphite as lithium ion battery negative material the time.On the one hand, lithium ion inserts graphite layers and can make interlamellar spacing increase in charging process, and lithium ion deviates to make graphite layers apart from reducing in the discharge process, and circulation repeatedly back graphite-structure can be because harmomegathus and destroyed repeatedly, so its cycle life is shorter; On the other hand, because the graphite surface carbon atom has a large amount of unsaturated bonds, electrolyte can decompose and formation SEI (Solid Electrolyte Interface) film at graphite surface when initial charge, makes that irreversible first amount is bigger, reduces cycle efficieny.
In order to improve cycle life and to improve cycle efficieny first, method after deliberation and its pluses and minuses are as follows:
1) utilize oxidant such as hydrogen peroxide to carry out the surface oxidation modification: the advantage method is easy, but that performance improves is limited.
2) utilizing organic substance to carry out the surface coats and high temperature cabonization: advantage is that cycle efficieny raising first is bigger, and shortcoming is that cycle life is still lower.
3) mixing lithium handles: advantage is that cycle efficieny is first increased, and shortcoming is that cycle life is not had improvement.
4) in conjunction with above method duplex surface modification: advantage is that combination property improves a lot, but cycle life still has much room for improvement.
Tsing-Hua University's new carbon group has been carried out the research of this respect very early, and is used for the method for lithium ion battery negative material after finding this low cost, the little swollen graphite of high performance preparation and coating processing.
Summary of the invention
The present invention is directed to graphite cathode material because the unsaturated bond of surface carbon atom causes irreversible first amount high and discharge and recharge the harmomegathus effect that causes and destroy the problem that the negative electrode film structure makes the cycle performance difference, propose two technical schemes: with constitutionally stable amorphous carbon coated graphite surface with the irreversible first amount of reduction; Slowly take off to be inserted in the graphite granule with compound between graphite layers and form nano-micrometre level space, reserve the harmomegathus space, to improve cycle performance.
The carbonaceous lithium ion battery negative electrode material of a kind of nucleocapsid structure that the present invention proposes, granularity is 5～50 μ m, it is characterized in that: this negative material partly is made up of nuclear part and shell, the graphite that described nuclear part obtains after inserting for compound between graphite layers takes off, the amorphous carbon that described shell partly obtains for the organic substance pyrolysis.
In above-mentioned carbonaceous lithium ion battery negative electrode material, the graphite preparation method of described nuclear part is:
(1) chooses compound between graphite layers micro mist or the metal chloride MCl that raw material is the synthetic sour intercalation of chemical method or electrochemical process
xThe compound between graphite layers micro mist of intercalation, granularity are 5～50 μ m;
(2) raw material compound between graphite layers micro mist is taken off slowly slotting, describedly take off that to insert temperature be 50～350 ℃, the time is 12～72 hours, and described volumetric expansion of taking off the graphite volume ratio compound between graphite layers raw material after inserting is less than or equal to 50%.
In above-mentioned carbonaceous lithium ion battery negative electrode material, the acid of described sour intercalation comprises nitric acid, sulfuric acid, phosphoric acid, perchloric acid, various organic acids and composition thereof; Described metal chloride MCl
xM in the intercalation comprises Fe, Co, Ni, Cu, Zn, Sn, and x is 2 or 3 according to the metal valence state; The graphite that described intercalation is used is natural flake graphite, natural micro crystal graphite or electrographite.
In above-mentioned carbonaceous lithium ion battery negative electrode material, the preparation method of the shell of described amorphous carbon part is:
(1) be presoma with resin, carbohydrate, described resin is phenolic resins, furfural resin, furfural acetone resin, epoxy resin; Described carbohydrate is sugar, starch; The phosphorus content of described presoma is greater than 30%;
(2) above-mentioned presoma is dissolved in ethanol or water, makes the precursor solution of concentration 3～30wt%;
(3) graphite microparticles that will take off after inserting is dipped in the precursor solution of step 2, fully stirs, and filters redundant solution .100～300 ℃ drying;
(4) with the charing under inert gas shielding of the graphite powder behind the above-mentioned impregnation drying, be warming up to 700～1100 ℃ with 30～500 ℃/h speed, be incubated 0.5～5 hour, with the stove cooling, obtain the surface and have the graphite microparticles that amorphous carbon coats.
In the shell preparation method partly of above-mentioned amorphous carbon, described step 3 is to be 20～70wt% precursor solution with concentration to be made into mass ratio be solution with taking off graphite microparticles after inserting: graphite=1: the slurry of (0.5～0.1) by spraying moulding drying, becomes the graphite powder that coats presoma.
The carbonaceous lithium ion battery negative electrode material of the nucleocapsid structure that the present invention proposes has high power capacity, the low advantage of irreversible capacity, high cycle efficieny and long circulation life first.
Description of drawings
Fig. 1 is the electrical property figure of the carbonaceous lithium ion battery negative electrode material of nucleocapsid structure of the present invention.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further:
1) with acid or metal chloride MCl
xBy chemistry or electrochemical process raw material graphite is carried out intercalation.The acid of intercalation comprises nitric acid, sulfuric acid, phosphoric acid, perchloric acid, various organic acids and composition thereof; The metal chloride MCl of intercalation
xM comprise Fe, Co, Ni, Cu, Zn, Sn, x is 2 or 3 according to the metal valence state.The graphite that intercalation is used is natural flake graphite, natural micro crystal graphite, electrographite.
2) the compound between graphite layers micro mist (granularity is 5～50 μ m) that obtains was slowly taken off slotting in 12～72 hours 50～350 ℃ of heating, obtain taking off the graphite after inserting.The volumetric expansion of taking off the graphite volume ratio compound between graphite layers raw material after inserting is smaller or equal to 50%.
3) be presoma with resin, carbohydrate, it is dissolved in ethanol or water, make the precursor solution of concentration 3～30wt%.Wherein resin is phenolic resins, furfural resin, furfural acetone resin, epoxy resin; Carbohydrate is sugar, starch.The phosphorus content of presoma is greater than 30%.
4) graphite microparticles that will take off after inserting is dipped in the precursor solution, fully stirs 0.5～6 hour, filters redundant solution, the graphite powder after 100～300 ℃ of dryings are flooded.
5) the graphite powder charing under inert gas shielding after will flooding is warming up to 700～1100 ℃ with 30～500 ℃/h speed, is incubated 0.5～5 hour, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Perhaps adopt the precursor solution of 20～70wt% concentration and take off slotting back graphite powder and be made into mass ratio 1: (0.5～0.1) (solution: slurry graphite), by spraying moulding drying, become the graphite powder that coats presoma, then adopt identical charing method to prepare the graphite microparticles that amorphous carbon coats.
A) the common H for preparing of chemical method
2SO
4-H
2O
2It is 5～50 μ m that the system expansible graphite is crushed to particle diameter.
B) compound between graphite layers that obtains is heated 48h down at 250 ℃, slowly take off slotting.
C) the phenolic resins ethanolic solution of configuration 3wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 6 hours, leaves standstill filtration, the graphite powder behind 300 ℃ of dry filters 4 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 300 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
The surface that the method obtains have graphite microparticles that amorphous carbon coats first cycle efficieny to change test result greater than 90%, 38 cyclic discharge capacity as follows:
A) FeCl for preparing of electrochemical process
3It is 5～50 μ m that the intercalation expansible graphite is crushed to particle diameter.
B) compound between graphite layers that obtains is heated 72h down at 350 ℃, slowly take off slotting.
C) aqueous sucrose solution of configuration 20wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 0.5 hour, leaves standstill filtration, the graphite powder behind 100 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 700 ℃ with 500 ℃/h speed under nitrogen protection, is incubated 0.5 hour, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
A) the crystalline flake graphite micro mist of 5～50 μ m particle diameters adopts chemical method to prepare H
2SO
4The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 12h down at 205 ℃, slowly take off slotting.
C) the phenolic resins ethanolic solution of configuration 5% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 2 hours, leaves standstill filtration, the graphite powder behind 200 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 250 ℃/h speed under nitrogen protection, is incubated 3 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
A) the micro crystal graphite micro mist of 5～50 μ m particle diameters uses electrochemical production FeCl
3The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 50h down at 300 ℃, slowly take off slotting.
C) amidin of configuration 30wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 3 hours, leaves standstill filtration, the graphite powder behind 100 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 900 ℃ with 200 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
A) the electrographite micro mist of 5～50 μ m particle diameters uses electrochemical process to prepare CuCl
2The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 50h down at 300 ℃, slowly take off slotting.
C) aqueous sucrose solution of configuration 20wt% mass fraction, the graphite that will take off after inserting immerses in the solution, stirs 60 minutes, leaves standstill filtration, the graphite powder behind 100 ℃ of dry filters 6 hours.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 300 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
A) the crystalline flake graphite micro mist of 5～50 μ m particle diameters adopts chemical method to prepare H
2SO
4The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 50h down at 205 ℃, slowly take off slotting.
C) the phenolic resins ethanolic solution of configuration 70wt% concentration is inserted the back graphite powder and was made into mass ratio 1: 0.5 (solution: slurry graphite) by spraying moulding drying, becomes the graphite powder that coats presoma with taking off.
D) graphite powder that previous step is obtained suddenly is warming up to 1000 ℃ with 50 ℃/h speed under nitrogen protection, is incubated 4 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
A) the crystalline flake graphite micro mist of 5～50 μ m particle diameters adopts chemical method to prepare HNO
3The intercalated graphite intercalation compound.
B) compound between graphite layers that obtains is heated 24h down at 50 ℃, slowly take off slotting.
C) the furfural acetone resin ethanolic solution of configuration 20wt% concentration is inserted the back graphite powder and was made into mass ratio 1: 0.1 (solution: slurry graphite) by spraying moulding drying, becomes the graphite powder that coats presoma with taking off.
D) graphite powder that previous step is obtained suddenly is warming up to 1100 ℃ with 500 ℃/h speed under argon shield, is incubated 5 hours, with the stove cooling, obtains the graphite microparticles that the surface has amorphous carbon to coat.
Claims (4)
1. the carbonaceous lithium ion battery negative electrode material of a nucleocapsid structure, granularity is 5～50 μ m, it is characterized in that: this negative material partly is made up of nuclear part and shell, the graphite that described nuclear part obtains after inserting for compound between graphite layers takes off, described compound between graphite layers is the compound between graphite layers micro mist or the metal chloride MCl of sour intercalation
xThe compound between graphite layers micro mist of intercalation, M comprises Fe, Co, Ni, Cu, Zn or Sn, x is 2 or 3 according to the metal valence state, the amorphous carbon that described shell partly obtains for the organic substance pyrolysis, described organic substance are phosphorus content greater than 30% phenolic resins, furfural resin, furfural acetone resin, epoxy resin, sucrose or starch.
2. carbonaceous lithium ion battery negative electrode material according to claim 1 is characterized in that, the graphite preparation method of described nuclear part is:
(1) choose the compound between graphite layers micro mist that raw material is the synthetic sour intercalation of chemical method or electrochemical process or the compound between graphite layers micro mist of metal chloride intercalation, granularity is 5～50 μ m;
(2) raw material compound between graphite layers micro mist is taken off slowly slotting, take off that to insert temperature be 50～350 ℃, the time is 12～72 hours, and the volumetric expansion of taking off the graphite volume ratio compound between graphite layers raw material after inserting is less than or equal to 50%.
3. carbonaceous lithium ion battery negative electrode material according to claim 2 is characterized in that, the acid that sour intercalation uses comprises the mixture of nitric acid, sulfuric acid, phosphoric acid, perchloric acid, organic acid or aforementioned acid; The graphite that intercalation is used is natural flake graphite, natural micro crystal graphite or electrographite.
4. carbonaceous lithium ion battery negative electrode material according to claim 1 is characterized in that, the preparation method of the shell part of amorphous carbon is:
(1) be presoma with resin or carbohydrate, described resin is phenolic resins, furfural resin, furfural acetone resin or epoxy resin; Described carbohydrate is sucrose or starch; The phosphorus content of described presoma is greater than 30%;
(2) above-mentioned presoma is dissolved in ethanol or water, makes the precursor solution of concentration 3～30wt%;
(3) graphite microparticles that will take off after inserting is dipped in the precursor solution of step 2, fully stirs, and filters redundant solution, 100～300 ℃ of dryings;
(4) with the charing under inert gas shielding of the graphite powder behind the impregnation drying that obtains in the step 3, be warming up to 700～1100 ℃ with 30～500 ℃/h speed, be incubated 0.5～5 hour, with the stove cooling, make the graphite microparticles surface coat the shell of going up amorphous carbon.
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| CN101771146B (en) | 2009-01-07 | 2012-08-29 | 清华大学 | Lithium ion battery anode material and preparation method thereof |
| CN101527357B (en) * | 2009-04-24 | 2012-05-16 | 清华大学 | Nano-silicon amorphous carbon composition lithium ion battery cathode material and preparation method therefor |
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| CN107256806B (en) * | 2017-06-23 | 2019-09-24 | 中国科学院宁波材料技术与工程研究所 | A kind of electrode material and supercapacitor |
| CN109616638B (en) * | 2018-12-05 | 2020-08-25 | 中南大学 | Spherical core-shell structure mixed graphite @ hard carbon composite material and preparation method and application thereof |
| CN109742356A (en) * | 2018-12-29 | 2019-05-10 | 湖南中科星城石墨有限公司 | A kind of preparation method of graphite cathode material |
| CN112490443A (en) * | 2019-09-12 | 2021-03-12 | 宁波杉杉新材料科技有限公司 | Liquid-phase-coated graphite negative electrode material and preparation method thereof |
| CN110743571B (en) * | 2019-12-03 | 2021-04-13 | 清华大学 | By using H2Method for preparing carbon-supported Pt shell core catalyst by liquid phase reduction |
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Application publication date: 20061018 Assignee: Wulanchabu Dasheng Graphite New Material Co., Ltd. Assignor: Tsinghua University Contract record no.: 2016150000001 Denomination of invention: Carbonaceous lithium ion battery negative electrode material with nuclear shell structure and producing method thereof Granted publication date: 20080820 License type: Common License Record date: 20160315 |
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