CN100347887C - Composite graphite negative electrode material for lithium ion secondary cell and its preparation method - Google Patents
Composite graphite negative electrode material for lithium ion secondary cell and its preparation method Download PDFInfo
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Abstract
The present invention discloses a negative electrode material compounded with graphite of a lithium ion secondary cell and a preparation method thereof, which aims to achieve the technical purposes of high discharge capacity of a negative electrode material, high coulomb efficiency of the negative electrode material and long cycle life of the negative electrode material. The negative electrode material compounded with graphite of a lithium ion secondary cell of the present invention comprises modified natural graphite and artificial graphite; the mass ratio of the modified natural graphite and the artificial graphite is from 30: 70 to 80: 20. The preparation method comprises the steps: 1. an organic substance is coated with the surface of the natural graphite; 2. heat treatment is carried out to the coated graphite for 1 to 6 hours within the temperature range of 800 DEG C to 1500 DEG C; 3. the modified natural graphite and the artificial graphite are mixed according to the mass ratio of 30: 70 to 80: 20. Compared with the prior art, the negative electrode material of the present invention, in which kernel and shell structure graphite formed by the compound of the natural graphite with an amorphous carbon material is mixed with the artificial graphite; therefore, the respective advantages of the natural graphite and the artificial graphite can be fully played; a lithium ion secondary cell which uses the materials as a negative electrode has high discharge capacity, good cycle performance and low production cost.
Description
Technical field
The present invention relates to a kind of composite graphite negative electrode material that is used for lithium rechargeable battery and preparation method thereof.
Background technology
Lithium ion battery has been the secondary cell of new generation after Ni-MH battery since the eighties of last century the nineties.Because of its have operating voltage height, energy density big, have extended cycle life, advantages such as self discharge is little, memory-less effect, become the chemical power source of present high-grade consumer electronics first-selection, and be penetrated into sophisticated technology fields such as Aero-Space, military affairs.Be accompanied by the demand that it grows with each passing day, lithium ion battery is just becoming the emphasis and the focus of new century scientific and technical research and exploitation.At present the negative material of commercialization lithium ion battery is material with carbon element, mainly is oil coke and graphite type material, wherein the charge/discharge capacity of native graphite Yin Qigao, favorable charge-discharge platform, wide material sources, cost is low and be used widely.But because the degree of graphitization of native graphite is higher, the edge of its crystallite and the crystal structure between the bottom surface and other physicochemical properties difference are bigger, stronger with the inhomogeneities of electrolyte reaction, and the decomposition reaction of electrolyte mainly occurs in the marginal portion of crystallite.So the compactness of the passivating film that generates is relatively poor, in charging process, the common embedding of solvation lithium ion takes place easily, causes the expansion and the collapse of graphite linings, has increased irreversible capacity.After native graphite is handled through physics or chemical method in addition, exist the shortcoming with the adhesive property difference of pole plate, be easy to come off in the cycle charge discharge electric process, influenced cycle life, the cycle life when especially having reduced high current charge-discharge from pole plate.On the other hand, negative material as lithium ion battery, native graphite must increase its surface area to store more lithium through pulverizing, for the embedding that makes lithium ion, deviate from reaction and carry out smoothly, graphite powder must be broken to below 100 microns, and graphite is as a kind of lubriation material, be easy to take place interformational sliding, cause graphite in crushing process, to produce the change and the destruction of crystal structure, thereby influenced the charge/discharge capacity and the high rate during charging-discharging of graphite material, limited the extensive use of natural graphite negative electrode material.
In order to improve the chemical property of natural graphite material, people carry out physical and chemical modified and finishing by the whole bag of tricks to native graphite, and obtained corresponding effects, as native graphite is pulverized, classification and be processed into spheric granules, improved tap density, adopt the method for various surface modifications to improve the chemical property of graphite in addition in addition, a kind of employing thermal oxidation graphite powder is disclosed as Japan Patent No.2000-261046, change the surface state of graphite powder, though improved the reactivity of negative material and electrolyte, discharge capacity is lower than native graphite.United States Patent (USP) U.S.Pat.No.6403259 discloses a kind of employing and has ground native graphite or Delanium surface coating one deck material with carbon element, improved the high temperature self-discharge performance and the cryogenic property of negative material, but otherwise performance is not fully up to expectations.Also have United States Patent (USP) U.S.Pat.No.5908715 to adopt organic solvent dissolution epoxy resin, polyparaphenylene to coat pyrolytic carbon in addition at graphite surface, Chinese patent CN1224251A adopts ethanol dissolving phenolic resins or Lauxite coated graphite, Chinese patent CN1304187A is with the organic solvent solution coated graphite of polyacrylonitrile, Kynoar, epoxy resin etc., there is environmental pollution in said method, coat that the back graphite granule is easy to bond and pulverization process afterwards in be easy to cause the breakage that comes off of coating layer, influenced the overall performance of negative material.
Summary of the invention
The purpose of this invention is to provide composite graphite negative electrode material of a kind of lithium rechargeable battery and preparation method thereof, the technical problem that solve is to make negative material have high discharge capacity, coulombic efficiency and long cycle life, simplifies manufacture craft.
The present invention is by the following technical solutions: a kind of composite graphite negative electrode material of lithium rechargeable battery, and described graphite comprises modified natural graphite and Delanium, its mass ratio is 30: 70～80: 20.
Modified natural graphite of the present invention comprises the low-crystallinity turbostratic carbon shell of native graphite and coated natural graphite.
The average grain diameter of modified natural graphite of the present invention between 5～35 μ m, crystal layer spacing d
002At 0.335nm between the 0.346nm; The average grain diameter of described Delanium between 2～20 μ m, crystal layer spacing d
002At 0.336nm between the 0.362nm.
Native graphite average grain diameter of the present invention is 5～35 μ m, and tap density is 0.95～1.05g/ml, and specific area is 4.0～7.5m
2/ g.
A kind of preparation method of composite graphite negative electrode material of lithium rechargeable battery, may further comprise the steps: one, adopt liquid phase coating, fusion coating or solid phase mixing to coat method on the native graphite surface, coat furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, coke, coal tar pitch or petroleum asphalt, obtain coated graphite; Two,, examined, the modified natural graphite of shell structure with coated graphite heat treatment 1～6 hour in 800 ℃～1500 ℃ temperature ranges; Three, modified natural graphite is mixed with the mass ratio of Delanium according to 30: 70～80: 20.
When the present invention heat-treats described coated graphite, charge into protective gas.
Protective gas of the present invention is nitrogen, argon gas, helium, neon or carbon dioxide.
After the heat treatment of the present invention, cool to room temperature, pulverize, sieve.
The present invention compared with prior art, negative material adopts nuclear, the shell structure graphite of the compound amorphous carbon material gained of native graphite to mix with Delanium, can give full play to native graphite and Delanium advantage separately, with the lithium rechargeable battery discharge capacity height of this material as cathode, cycle performance is good and have lower production cost, and technology is simple, is easy to industrialization.
Description of drawings
Fig. 1 is the electromicroscopic photograph of the composite graphite negative electrode material of lithium rechargeable battery of the present invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.As shown in Figure 1, the composite graphite negative electrode material of lithium rechargeable battery of the present invention is mixed by nuclear, the modified natural graphite of shell structure and the Delanium mass ratio with 30: 70～80: 20, wherein modified natural graphite is made up of native graphite and the low-crystallinity turbostratic carbon shell that coats it, its average grain diameter between 5～35 μ m, crystal layer spacing d
002Between 0.335nm～0.346nm, it is 5～35 μ m that native graphite has average grain diameter, and tap density is 0.95～1.05g/ml, and specific area is 4.0～7.5m
2/ g, the predecessor that coats carbon-coating is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, coke, coal tar pitch or petroleum asphalt.The average grain diameter of Delanium between 2～20 μ m, crystal layer spacing d
002At 0.336nm between the 0.362nm.
In the present invention, the average grain diameter of coating modification native graphite is between 5～35 μ m, the average grain diameter of Delanium is between 2～20 μ m, the two exists complementary on particle size, can make like this and fill short grained Delanium between the oarse-grained modified natural graphite, further optimizing the microcosmic of graphite particle in the negative material arranges, improve tap density and the compacted density of pole piece and the bond strength between the negative material particle, reduce exfoliated in the repeated charge process, not only improve the reversible capacity and the cycle life of battery, and improved the security performance of high current charge-discharge ability and battery.
The crystal layer spacing d of coating modification native graphite in the composite graphite negative electrode material of the present invention
002At 0.335nm between the 0.346nm, the crystal layer spacing d of Delanium
002At 0.336nm between the 0.362nm, the coating modification native graphite has less crystal layer spacing and higher degree of crystallinity, Delanium in contrast, can give full play to advantages separately such as good cyclical stability that native graphite has higher charge/discharge capacity and Delanium, high rate during charging-discharging like this, thus the negative material that obtains having excellent comprehensive performances.
All La, the Lc than Delanium is big for the ulking thickness Lc of the carbon atom aspect size La of coating modification native graphite and carbon atom aspect in the composite graphite negative electrode material that the present invention relates to, also be based on a kind of like this thought, promptly the coating modification native graphite of big crystallite size has higher lithium storage content, the native graphite of less crystallite size then in the cyclic process not easy fracture pulverize, stable circulation, life-span are long, the two complements one another, have complementary advantages, realize effective lifting of composite graphite negative electrode material overall performance.In actual applications, composite modified native graphite and the mixing quality of Delanium are than reaching best result of use at 30: 70～80: 20.
The preparation method of the composite graphite negative electrode material of lithium rechargeable battery of the present invention may further comprise the steps: one, adopt liquid phase coating, fusion coating and solid phase mixing method for coating to coat organic substance on the native graphite surface, obtain coated graphite; Two, with coated graphite heat treatment 1～6 hour in 800 ℃～1500 ℃ temperature ranges, during heat treatment, charge into protective gas; Three, after the heat treatment, cool to room temperature, pulverize, sieve, examined, the modified natural graphite of shell structure; Four, modified natural graphite is mixed with the mass ratio of Delanium according to 30: 70～80: 20.
Organic substance is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, coke, coal tar pitch or petroleum asphalt; Protective gas is nitrogen, argon gas, helium, neon or carbon dioxide.
Utilize the composite graphite negative electrode material of lithium rechargeable battery of the present invention to prepare the negative pole of battery, adopt above-mentioned negative material to add binding agent, thickener and solvent, carry out stirring pulping, be coated on the Copper Foil, through oven dry, roll and make.Used binding agent can be the LA-133 that the Kynoar PVDF that is dissolved in the N-methyl pyrrolidone, water miscible butadiene-styrene rubber newborn SBR, sodium carboxymethylcellulose CMC, Chengdu organic chemistry are produced.Used positive electrode can be the various composite oxides that contain lithium ion, as: LiCoO
2, LiNiO
2Or LiMn
2O
4, used electrolyte can adopt general various electrolyte and solvent, and electrolyte can be inorganic electrolyte and organic bath, as LiClO
4, LiPF
6, LiAsF
6, LiBF
6Or Li (CF
3SO
2)
2N, solvent are generally mixed by the carbonic acid cyclenes ester and the low viscous chain hydrocarbon carbonic ester of high-k, as ethylene carbonate EC, propene carbonate PC, dimethyl carbonate DMC, diethyl carbonate DEC or methyl ethyl carbonate MEC etc.Use composite graphite negative electrode material of the present invention to make the used barrier film of lithium ion battery without limits, can use commercially available polythene PE, polypropylene PP or poly-second propylene PEP composite membrane.
The present invention is by coating the material with carbon element of low-crystallinity at graphite surface, and with this material and the mixed composite graphite that gets of Delanium, the lithium rechargeable battery of making negative pole with this composite graphite has that discharge capacity height, cycle performance are good, good heavy current and lower production cost, and technology is simple, is easy to industrialization.
Embodiment 1:
The fire stons oil asphalt is crushed to below the 3 μ m, with average grain diameter D in the high softening-point
50=17.931 μ m, tap density 1.017g/cm
3, specific area 5.3m
2The spherical natural graphite of/g fully mixes bonding with asphalt powder, and pitch is 1: 10 with the mixing quality ratio of native graphite; Again with above-mentioned coated graphite under protection of nitrogen gas, be warming up to 1100 ℃ the insulation 2 hours, reduce to room temperature, obtain the coating modification native graphite, its average grain diameter D
50Be 18.4 μ m, crystal layer spacing d
002Be 0.3358nm.Above-mentioned coated graphite mixes with the mass ratio of Delanium according to 50: 50 after crushing and screening, and as the composite graphite negative electrode material of lithium ion battery of the present invention, wherein Delanium has average grain diameter D
50Be 12.4 μ m, crystal layer spacing d
002Be 0.3368nm.
Embodiment 2:
Pitch powder is broken to below the 3 μ m, with average grain diameter D
50=4.8 μ m, tap density 0.95g/cm
3, specific area 7.5m
2The spherical natural graphite of/g fully mixes bonding with asphalt powder, and pitch is 1: 10 with the mixing quality ratio of native graphite; Again with above-mentioned coated graphite under the protection of argon gas, be warming up to 800 ℃ the insulation 6 hours, reduce to room temperature, obtain the coating modification native graphite, its average grain diameter D
50Be 5 μ m, crystal layer spacing d
002Be 0.335nm.Above-mentioned coated graphite mixes with the mass ratio of Delanium according to 30: 70 after crushing and screening, and as the composite graphite negative electrode material of lithium ion battery of the present invention, wherein Delanium has average grain diameter D
50Be 2 μ m, crystal layer spacing d
002Be 0.336nm.
Embodiment 3:
Furane resins are crushed to below the 3 μ m, with average grain diameter D
50=34.6 μ m,, tap density 1.05g/cm
3, specific area 4.0m
2The spherical natural graphite of/g fully mixes bonding with the furane resins powder, and furane resins are 1: 10 with the mixing quality ratio of native graphite; Again with above-mentioned coated graphite under the protection of helium, be warming up to 1500 ℃ the insulation 1 hour, reduce to room temperature, obtain the coating modification native graphite, its average grain diameter D
50Be 35 μ m, crystal layer spacing d
002Be 0.346nm.Above-mentioned coated graphite mixes with the mass ratio of Delanium according to 40: 60 after crushing and screening, and as the composite graphite negative electrode material of lithium ion battery of the present invention, wherein Delanium has average grain diameter D
50Be 20 μ m, crystal layer spacing d
002Be 0.362nm.
Embodiment 4:
Polyvinyl alcohol is crushed to below the 3 μ m, with average grain diameter D
50=18.1 μ m,, tap density 1.021g/cm
3, specific area 5.2m
2The spherical natural graphite of/g fully mixes bonding with pva powder, and polyvinyl alcohol is 1: 10 with the mixing quality ratio of native graphite; Again with above-mentioned coated graphite under the protection of neon, be warming up to 1100 ℃ the insulation 2 hours, reduce to room temperature, obtain the coating modification native graphite, its average grain diameter D
50Be 18.4 μ m, crystal layer spacing d
002Be 0.3358nm.Above-mentioned coated graphite mixes with the mass ratio of Delanium according to 60: 40 after crushing and screening, and as the composite graphite negative electrode material of lithium ion battery of the present invention, wherein Delanium has average grain diameter D
50Be 12.4 μ m, crystal layer spacing d
002Be 0.3368nm.
Embodiment 5:
Phenolic resins is crushed to below the 3 μ m, with average grain diameter D
50=18.1 μ m,, tap density 1.021g/cm
3, specific area 5.2m
2The spherical natural graphite of/g fully mixes bonding with the phenolic resins powder, and phenolic resins is 1: 10 with the mixing quality ratio of native graphite; Again with above-mentioned coated graphite under the protection of carbon dioxide, be warming up to 1100 ℃ the insulation 2 hours, reduce to room temperature, obtain the coating modification native graphite, its average grain diameter D
50Be 18.4 μ m, crystal layer spacing d
002Be 0.3358nm, specific area 1.5m
2/ g, above-mentioned coated graphite mix with the mass ratio of Delanium according to 80: 20 after crushing and screening, and as the composite graphite negative electrode material of lithium ion battery of the present invention, wherein Delanium has average grain diameter D
50Be 12.4 μ m, crystal layer spacing d
002Be 0.3368nm.
Comparative example 1:
Native graphite is handled according to the same method of embodiment 1, is not mixed afterwards with Delanium, with this coated graphite directly as lithium ion battery negative material.
Comparative example 2:
With the Delanium among the embodiment 1 directly as lithium ion battery negative material.
Comparative example 3:
Native graphite among the embodiment 1 is not coated processing, mix the negative material of back according to 50: 50 mass ratio as lithium ion battery with Delanium.
The physical property test specific area of negative material adopts the BET method of nitrogen replacement to measure, average grain diameter is measured by Britain Malvern-Mastersizer 2000 laser particle size analyzers, and the crystal layer spacing is measured by Japan's motor D of science/Max-IIIA X-ray (powder) diffractometer.
Lithium ion battery negative material that electrochemical property test makes the foregoing description and comparative example respectively and water-soluble binder LA133, conductive agent, are applied on the Copper Foil collector electrode than mixed pulp according to 96: 3: 1 quality, after the vacuumize as negative pole; Adopt conventional production process assembling finished product battery, positive electrode is selected LiCoO for use
2, use 1MLiPF
6EC/DMC/MEC solution be electrolyte, barrier film is the PE/PP/PE composite membrane, and battery is carried out following testing performance index:
Initial charge specific capacity: with the electric current initial charge of 0.2C charging capacity/negative electrode active material quality to 4.2v;
First discharge specific capacity: the discharge capacity/negative electrode active material quality that is discharged to 3.0v with the electric current of 0.2C first;
First charge-discharge efficiency=(initial charge capacity/discharge capacity) first * 100%.
Cycle performance test: with the current charges of 1C to 4.2v, again with the current discharge of 1C to 3.0v;
100 all capability retentions=(discharge capacity of discharge capacity/first of the 100th circulation) * 100%.
The heavy-current discharge performance test:
C
2C/ C
0.5C=(discharging into the discharge capacity of 3.0v/discharge into from the 4.2v discharge capacity of 3.0v from 4.2v) * 100% with the electric current of 0.5C with the electric current of 2C.
Test result is listed in table 1.
Table 1. electrochemical property test result
| Sequence number | Coated graphite: Delanium | Initial charge specific capacity mAh/g | First discharge specific capacity mAh/g | First charge-discharge efficiency % | 100 all circulation volume conservation rate % | Heavy-current discharge performance C 2C/C 0.5C ％ |
| Embodiment 1 | 50∶50 | 383 | 359 | 93.7 | 94.2 | 93.8 |
| Embodiment 2 | 30∶70 | 389 | 351 | 89.3 | 95.3 | 93.1 |
| Embodiment 3 | 40∶60 | 379 | 349 | 92.1 | 95.8 | 91.9 |
| Embodiment 4 | 60∶40 | 383 | 355 | 92.6 | 95.7 | 93.7 |
| Embodiment 5 | 80∶20 | 389 | 363 | 93.4 | 96.2 | 95.4 |
| Comparative example 1 | 100∶0 | 385 | 360 | 93.5 | 91.0 | 91.5 |
| Comparative example 2 | 0∶100 | 353 | 322 | 91.2 | 95.4 | 90.1 |
| Comparative example 3 | Not 50 (not coating): 50 | 389 | 345 | 88.7 | 83.2 | 82.1 |
Native graphite by coating modification mixes as lithium ion battery negative material with Delanium, has good electrochemistry combination property, its first discharging efficiency reach 89.3%～93.7%; 100 all circulation volume conservation rates are more than 94%, and have good large current discharging capability.
Claims (7)
1. the composite graphite negative electrode material of a lithium rechargeable battery, it is characterized in that: described graphite comprises modified natural graphite and Delanium, its mass ratio is 30: 70～80: 20, and modified natural graphite comprises the low-crystallinity turbostratic carbon shell of native graphite and coated natural graphite.
2. the composite graphite negative electrode material of lithium rechargeable battery according to claim 1 is characterized in that: the average grain diameter of described modified natural graphite between 5～35 μ m, crystal layer spacing d
002At 0.335nm between the 0.346nm; The average grain diameter of described Delanium between 2～20 μ m, crystal layer spacing d
002At 0.336nm between the 0.362nm.
3. the composite graphite negative electrode material of lithium rechargeable battery according to claim 2, it is characterized in that: described native graphite average grain diameter is 5～35 μ m, and tap density is 0.95～1.05g/ml, and specific area is 4.0～7.5m
2/ g.
4. the preparation method of the composite graphite negative electrode material of a lithium rechargeable battery, may further comprise the steps: one, adopt liquid phase coating, fusion coating or solid phase mixing to coat method on the native graphite surface, coat furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, coke, coal tar pitch or petroleum asphalt, obtain coated graphite; Two,, examined, the modified natural graphite of shell structure with coated graphite heat treatment 1～6 hour in 800 ℃～1500 ℃ temperature ranges; Three, modified natural graphite is mixed with the mass ratio of Delanium according to 30: 70～80: 20.
5. the preparation method of the composite graphite negative electrode material of lithium rechargeable battery according to claim 4 is characterized in that: when described coated graphite is heat-treated, charge into protective gas.
6. the preparation method of the composite graphite negative electrode material of lithium rechargeable battery according to claim 5, it is characterized in that: described protective gas is nitrogen, argon gas, helium, neon or carbon dioxide.
7. the preparation method of the composite graphite negative electrode material of lithium rechargeable battery according to claim 6 is characterized in that: after the described heat treatment, cool to room temperature, pulverize, sieve.
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| CN1702892A (en) | 2005-11-30 |
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