CN1079588C - Lithium-ion secondary cell and mfg. method therefor - Google Patents
Lithium-ion secondary cell and mfg. method therefor Download PDFInfo
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- CN1079588C CN1079588C CN97115263A CN97115263A CN1079588C CN 1079588 C CN1079588 C CN 1079588C CN 97115263 A CN97115263 A CN 97115263A CN 97115263 A CN97115263 A CN 97115263A CN 1079588 C CN1079588 C CN 1079588C
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- negative pole
- rechargeable battery
- negative
- preparation
- lithium rechargeable
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a lithium ion secondary battery and a preparation method thereof, particularly to a lithium ion battery. The negative electrode material of the lithium ion battery is the carbon material of thermal depolymerization p-phenylene. A negative electrode is formed by mixing a hole-enlarging agent, a conductive agent and a binding agent, and a positive electrode is LiCoO2. The lithium ion secondary battery of the present invention has the advantages of high specific capacity, safe use and stable relative capacity by the cycle of charge and discharge.
Description
The present invention relates to a kind of lithium ion battery, particularly a kind of negative active core-shell material and preparation method thereof.
The key of lithium ion battery is the preparation of positive and negative electrode material, preparation specific capacity height, constitutionally stable positive and negative electrode material is many researchers' a target, petroleum coke and graphite is the negative material of Ceng Zuowei lithium ion after treatment, but their specific capacity is all not too high, the petroleum coke specific capacity is about 180mAh/g, and the specific capacity of graphite is up to 350mAh/g.Then development as negative active core-shell material, has obtained result preferably with macromolecule pyrolysis gained carbonaceous material.Wherein, Sci-ence1994 (264) 556 is reported in the hydrogen atmosphere in 700 ℃ of pyrolysis polyparaphenylenes, though the gained RESEARCH OF PYROCARBON first capacity reach 680mAh.g
-1, but with hydrogen as heat-treating atmosphere, the cost height, dangerous.And (J.Electrochem.Soc.1994 (11L
143) specific capacity of this RESEARCH OF PYROCARBON is very responsive to heat treatment temperature, capacity loses gradually in follow-up charge and discharge process.
It is low to the objective of the invention is to overcome in the existing lithium battery negative material specific capacity, and with hydrogen as heat-treating atmosphere shortcoming dangerous and that capacity loses gradually when discharging and recharging, and the lithium rechargeable battery that provides a kind of negative material of high specific capacity to constitute.
Lithium rechargeable battery of the present invention is made up of anodal, negative material electrolyte and barrier film, and wherein negative active core-shell material is the material with carbon element that benzene is obtained a kind of graphite and amorphous carbon mixing crystal formation by thermal depolymerization.Positive electrode is embedding lithium transition-metal oxide LiCoO
2, electrolyte is the mixed solution of 0.5-1.0 mol lithium salts, barrier film is nonwoven fabrics or microporous polypropylene membrane.
The preparation of negative material in the lithium rechargeable battery of the present invention:
1, with the H/C atomic ratio be the poly-of 0.2-0.8 to benzene, flow velocity be the 0.01-10 liter/minute N
2In the air-flow, be 2-40 ℃/minute with the programming rate, 600-1100 ℃ is preferably 700-900 ℃, and pyrolysis 0.5-48 hour, be preferably 8-12 hour, 1-35 ℃/minute speed is reduced to 20 ℃ then, makes the carbon negative active core-shell material.
2, with above-mentioned carbon negative pole material and expanding agent by weight 100: 1-40: 60 mixed, with carbon negative pole material, the percentage by weight sum of expanding agent conductive agent carbon black binding agent is to add the conductive agent of 0-20% and the binding agent of 0.1-15% at 100% o'clock, after the grinding evenly, makes electrode.
Described expanding agent is NH
4CL, (NH
4)
2CO
3, NH
4HCO
3, CO (NH
2)
2(NH
4)
2C
2O
4, described conductive agent is graphite or carbon black.
Described binding agent is a polytetrafluoroethylene, Kynoar.
The preparation of the electrolyte of lithium rechargeable battery of the present invention is 0.5-1.0 mol lithium salts to be dissolved in second (in propylene carbonate (EC or PC) and dimethyl diethylester mixing (DME) solvent, obtain electrolyte.
Barrier film of the present invention is the polypropylene porous material, after making lithium ion battery, after the battery charge, lithium ion embeds negative pole, but forms working battery, puts the charging measuring capacity continuously, in the weight of negative electrode active material, the reversible specific capacity of battery is between 350-454mhA.g
-1
Ion secondary battery cathode material lithium of the present invention has high specific capacity, this battery is safe in utilization, cost is low, have stable discharge voltage and relative capacity, see accompanying drawing 1,2, accompanying drawing 1 is the discharge curve of button cell 2025 models, and accompanying drawing 2 is the charge of button cell 2025 models.
To gather benzene at N
2Flow velocity is under 2 liters/minute, with 10 ℃/minute be warming up to 760 ℃ constant 4 hours, reduce to 25 ℃ with 10 ℃/minute then, obtain RESEARCH OF PYROCARBON, in RESEARCH OF PYROCARBON, add poly-tetrafluoro emulsion, add NH simultaneously
4HCO
3Making electrode, is to electrode with the lithium sheet, and vinyl carbonate and dimethyl diethylester are solvent, LiClO
4Be electrolyte, make the model battery, make cycle life and measure, reversible capacity is 750mAh/g for the first time, and the 20th time is 350mAh/g.
Embodiment 2,
To gather benzene at N
2Flow velocity is under 1 liter/minute, with 2 ℃/minute be warming up to 750 ℃ constant 12 hours, reduce to 25 ℃ with 10 ℃/minute then, obtain RESEARCH OF PYROCARBON, in RESEARCH OF PYROCARBON, add poly-tetrafluoro emulsion, make electrode, with the lithium sheet is to electrode, and vinyl carbonate and dimethyl diethylester are solvent, LiClO
4Be electrolyte, make the model battery, make cycle life and measure, reversible capacity is 720mAh/g for the first time, and the 20th time is 412mAh/g.
Embodiment 3,
To gather benzene at N
2Flow velocity is that 1l/ divides down, with 2 ℃/minute be warming up to 850 ℃ constant 8 hours, reduce to 25 ℃ with 10 ℃/minute then, obtain RESEARCH OF PYROCARBON, in RESEARCH OF PYROCARBON, add poly-tetrafluoro emulsion, make electrode, with the lithium sheet is to electrode, and vinyl carbonate and dimethyl diethylester are solvent, LiClO
4Be electrolyte, make the model battery, make cycle life and measure, reversible capacity is 640mAh/g for the first time, and the 20th time is 454mAh/g.
Embodiment 4,
The carbon that makes with embodiment 3 is as negative pole, with LiCoO
2Be positive pole, PC+DME+LiClO
4Be electrolyte, make 2025 type button cells, its weight is 2.5g, lies prostrate continuous 1mA through 2.5-3.6 and discharges and recharges, and capacity is 25mAh.Discharge and recharge through 5mA, 160 times circulation volume does not have significantly sacrificing.
Claims (5)
1, a kind of lithium rechargeable battery comprises positive pole, negative pole, electrolyte, barrier film, it is characterized in that described negative pole is the carbon negative active core-shell material that thermal depolymerization obtains benzene, described just very LiCoO
2, described electrolyte is the mixed solution of 0.5-1.0 mol lithium salts.
2. a kind of lithium rechargeable battery according to claim 1, the solvent that it is characterized in that described mixed solution are vinyl carbonate and dimethyl diethylester mixed solvent.
3. a kind of lithium rechargeable battery according to claim 1, the solvent that it is characterized in that described mixed solution are propylene carbonate and dimethyl diethylester mixed solvent.
4. the preparation method of a kind of lithium rechargeable battery according to claim 1 comprises the preparation of positive and negative electrode, it is characterized in that described negative pole in the following order step carry out:
(1) preparation of RESEARCH OF PYROCARBON negative material:
With poly-to benzene the 1-2 liter/minute N
2In the air-flow,, make carbon negative pole material at 700-900 ℃ of pyrolysis 8-12 hour,
(2) above-mentioned negative material is mixed by weight 1: 1 with expanding agent, percentage by weight sum with carbon negative pole material, expanding agent, conductive agent, carbon black, binding agent is 100% o'clock, adds the carbon black of 0.5-20% and the poly-tetrafluoro emulsion of 0.1-15% and makes negative pole.
5. the preparation method of a kind of lithium rechargeable battery according to claim 4 is characterized in that described expanding agent is NH
4HCO
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97115263A CN1079588C (en) | 1997-08-27 | 1997-08-27 | Lithium-ion secondary cell and mfg. method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97115263A CN1079588C (en) | 1997-08-27 | 1997-08-27 | Lithium-ion secondary cell and mfg. method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1209661A CN1209661A (en) | 1999-03-03 |
| CN1079588C true CN1079588C (en) | 2002-02-20 |
Family
ID=5173253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97115263A Expired - Fee Related CN1079588C (en) | 1997-08-27 | 1997-08-27 | Lithium-ion secondary cell and mfg. method therefor |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0831410A (en) * | 1994-07-13 | 1996-02-02 | Toshiba Battery Co Ltd | Lithium secondary battery |
| CN1126379A (en) * | 1994-11-03 | 1996-07-10 | 北京有色金属研究总院 | Carbon anode material for secondary lithium ion cell and prodn. method thereof |
-
1997
- 1997-08-27 CN CN97115263A patent/CN1079588C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0831410A (en) * | 1994-07-13 | 1996-02-02 | Toshiba Battery Co Ltd | Lithium secondary battery |
| CN1126379A (en) * | 1994-11-03 | 1996-07-10 | 北京有色金属研究总院 | Carbon anode material for secondary lithium ion cell and prodn. method thereof |
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| Publication number | Publication date |
|---|---|
| CN1209661A (en) | 1999-03-03 |
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