CN102723462A - Manufacture method of anode of lithium ion secondary battery - Google Patents
Manufacture method of anode of lithium ion secondary battery Download PDFInfo
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- CN102723462A CN102723462A CN2012102207021A CN201210220702A CN102723462A CN 102723462 A CN102723462 A CN 102723462A CN 2012102207021 A CN2012102207021 A CN 2012102207021A CN 201210220702 A CN201210220702 A CN 201210220702A CN 102723462 A CN102723462 A CN 102723462A
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- anode
- acetylene black
- cnt
- positive active
- active material
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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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Abstract
The invention discloses a manufacture method of an anode of a lithium ion secondary battery. The method includes the following steps: modulating positive active materials, binders, conductive agents and liquid dispersion media in mixing mode, coating anode slurry on two faces of a current collector for drying, conducting rolling on the anode slurry in the drying state and coated on the current collector through a roller and conducting shearing to form the anode of the lithium ion secondary battery. The conductive agents are composites composed of carbon nanometer tubes and acetylene black, and the positive active materials utilize LixMnaCo2-aO4 or LixMnaFe2-aO4.
Description
Technical field
The present invention relates to a kind of electrode manufacturing method, relate in particular to a kind of lithium ion secondary battery positive electrode manufacturing approach.
Background technology
Secondary cell, comprising can be through the active material that charges and regenerate.When energy that secondary cell produced is reduced to optimum efficiency when following, can be with them with any the recharging in many modes.Based on the chemical composition of battery, can rechargeable battery be subdivided into two primary categories.This two classifications, i.e. alkaline secondary cell and lithium secondary battery.Wherein lithium rechargeable battery is a kind of novel high-energy secondary power supply, has that specific capacity is big, discharge voltage is high and steady, advantages such as cryogenic property is good, environmental friendliness, safety, the life-span is long, self discharge is faint.The above-mentioned advantage of lithium rechargeable battery has caused various countries scientists' favor, thereby has promoted the fast development of lithium rechargeable battery.Since coming out, between the short more than ten years, lithium rechargeable battery just is widely used in the portable electronic products such as mobile phone, notebook computer, digital camera; Among the large-scale lithium rechargeable battery that fields such as some other key areas such as electric vehicle, Aero-Space, military affairs are used is also being developed.
Lithium rechargeable battery is made up of positive pole, negative pole, nonaqueous electrolyte etc., and wherein the positive pole of lithium rechargeable battery is for the significant effects that has of energy content of battery density, capacity and charge-discharge performance.
Summary of the invention
The manufacturing method for anode that the purpose of this invention is to provide a kind of lithium rechargeable battery of excellent performance.
To achieve these goals, the manufacturing method for anode of a kind of lithium rechargeable battery provided by the invention comprises the steps:
Step 1, make anode sizing agent: anode sizing agent is that positive active material, binding agent, conductive agent and aqueous decentralized medium hybrid modulation are formed.Wherein conductive agent is that CNT and acetylene black are formed compound, and described CNT is a multi-walled carbon nano-tubes, external diameter of pipe 10～60nm, and length is 10～100 μ m; The particle diameter of acetylene black is 20～50nm; Its preparation method is: a, take by weighing certain quantity of carbon nanometer pipe, acetylene black and dispersant, in water or organic solvent for ultrasonic dispersion CNT and acetylene black, process both total weight content and be 1～5% low concentration mother liquor; B, mother liquor separate water outlet or organic solvent through suction filtration or press filtration, obtain conductive agent after the drying.
Step 2 is coated onto the two sides of collector with anode sizing agent, carries out drying.Collector is provided with the blank portion that does not scribble anode sizing agent, and this blank portion is used for the lead welding.
Step 3, the anode sizing agent that spreads upon the drying regime on the collector through roll is rolled, and after the shearing, forms the positive pole of lithium rechargeable battery.
Wherein, positive active material uses Li
xMn
aCo
2-aO
4Or Li
xMn
aFe
2-aO
4(x=0.01～1, a=1.7～1.86).The particle diameter of positive active material is 2-30 μ m, and wherein the volume of the particle of 2-10 μ m accounts for more than 90%, and the specific area of positive active material is 0.2m when adopting the BET method
2/ g～1m
2/ g.
Preferably, the CNT in the step (1) adopts the CNT of 15～30nm, to help forming effective conductive network.
Compared with prior art, advantage of the present invention is: improved the charge-discharge performance of positive electrode through the improvement of conductive agent, through to improving of positive active material the capacity and the part throttle characteristics of electrode.
Embodiment
Embodiment one
Make the conductive agent that CNT and acetylene black are formed earlier, concrete technology is following: in 200ml deionized water or N-crassitude Chiung, add external diameter of pipe 20nm, length is the multi-walled carbon nano-tubes 3g of 10um, polyvinylpyrrolidone (PVP) 1.5g; After use has the ultrasonic dispersion of sonicated equipment of probe, add particle diameter 20nm acetylene black 6g again, continue ultrasonic dispersion, obtain the mother liquor of CNT and acetylene black.Mother liquor separates water outlet or organic solvent through suction filtration, obtains the conductive agent of being made up of CNT and acetylene black after the drying.
After having made conductive agent, with double-arm muller will be as positive active material, as the nmp solution of the PVdF of binding agent, stir as the CNT of conductive agent and acetylene black with as an amount of NMP of decentralized medium, process anode sizing agent.The mixing ratio of the conductive agent that solid shape part, CNT and the acetylene black of PVdF is formed, the cobalt acid lithium with respect to 100 weight portions is respectively 5 weight portions, 4 weight portions.Wherein positive active material uses Li
xMn
aCo
2-aO
4(x=0.01～1, a=1.7～1.86), its particle diameter is 2-30 μ m, and wherein the volume of the particle of 2-10 μ m accounts for more than 90%, and the specific area of positive active material is 0.2m when adopting the BET method
2/ g～1m
2/ g.
Then, anode sizing agent is coated on the two sides that thickness is the banded collector that is made up of aluminium foil of 15 μ m.Like this, make the anode sizing agent of coating dry, rolling with roll, shear the back and form lithium ion secondary battery positive electrode.
Embodiment two
Make the conductive agent that CNT and acetylene black are formed earlier, concrete technology is following: in 200ml deionized water or N-crassitude Chiung, add external diameter of pipe 60nm, length is the multi-walled carbon nano-tubes 4g of 50um, polyvinylpyrrolidone (PVP) 2g; After use has the ultrasonic dispersion of sonicated equipment of probe, add particle diameter 50nm acetylene black 8g again, continue ultrasonic dispersion, obtain the mother liquor of CNT and acetylene black.Mother liquor separates water outlet or organic solvent through suction filtration, obtains the conductive agent of being made up of CNT and acetylene black after the drying.
After having made conductive agent, with double-arm muller will be as positive active material, as the nmp solution of the PVdF of binding agent, stir as the CNT of conductive agent and acetylene black with as an amount of NMP of decentralized medium, process anode sizing agent.The mixing ratio of the conductive agent that solid shape part, CNT and the acetylene black of PVdF is formed, the cobalt acid lithium with respect to 100 weight portions is respectively 6 weight portions, 3 weight portions.Wherein positive active material uses Li
xMn
aFe
2-aO
4(x=0.01～1, a=1.7～1.86), its particle diameter is 2-30 μ m, and wherein the volume of the particle of 2-10 μ m accounts for more than 90%, and the specific area of positive active material is 0.2m when adopting the BET method
2/ g～1m
2/ g.
Then, anode sizing agent is coated on the two sides that thickness is the banded collector that is made up of aluminium foil of 12 μ m.Like this, make the anode sizing agent of coating dry, rolling with roll, shear the back and form lithium ion secondary battery positive electrode.
Comparative example one
Positive active material in the comparative example adopts cobalt acid lithium, and conductive agent adopts city commonly used to use the carbon black conductive agent, and other preparation technology is with embodiment one and two.
The battery (three kinds of batteries are except anodal difference, and miscellaneous part is all identical) that the positive pole of the lithium rechargeable battery that adopts embodiment one, embodiment two and comparative example one preparation is processed carries out performance test, and test result is following:
| ? | Discharge capacity (mAh/g) | Initial stage efficient (%) |
| Embodiment one | 348 | 90.3 |
| Embodiment two | 343 | 90.1 |
| Comparative example | 298 | 85.5 |
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in not breaking away from technical scheme of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be not break away from technical scheme content of the present invention, to any simple modification, equivalent variations and modification that above embodiment made, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (2)
1. the manufacturing method for anode of a lithium rechargeable battery, this method comprises the steps:
Step 1, make anode sizing agent: anode sizing agent is that positive active material, binding agent, conductive agent and aqueous decentralized medium hybrid modulation are formed; Wherein conductive agent is formed compound by CNT and acetylene black; Its preparation method is: a, take by weighing certain quantity of carbon nanometer pipe, acetylene black and dispersant; In water or organic solvent for ultrasonic dispersion CNT and acetylene black, process both total weight content and be 1～5% low concentration mother liquor; B, mother liquor separate water outlet or organic solvent through suction filtration or press filtration, obtain conductive agent after the drying; Wherein said CNT is a multi-walled carbon nano-tubes, external diameter of pipe 10～60nm, and length is 10～100 μ m; The particle diameter of acetylene black is 20～50nm;
Step 2 is coated onto the two sides of collector with anode sizing agent, carries out drying;
Collector is provided with the blank portion that does not scribble anode sizing agent, and this blank portion is used for the lead welding;
Step 3, the anode sizing agent that spreads upon the drying regime on the collector through roll is rolled, and after the shearing, forms the positive pole of lithium rechargeable battery;
It is characterized in that said positive active material uses Li
xMn
aCo
2-aO
4Or Li
xMn
aFe
2-aO
4(x=0.01～1, a=1.7～1.86), the particle diameter of said positive active material is 2-30 μ m, and wherein the volume of the particle of 2-10 μ m accounts for more than 90%, and the specific area of said positive active material is 0.2m when adopting the BET method
2/ g～1m
2/ g.
2. lithium ion secondary battery positive electrode manufacturing approach as claimed in claim 1, wherein, the CNT in the step (1) adopts the external diameter of pipe of 15～30nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102207021A CN102723462A (en) | 2012-06-29 | 2012-06-29 | Manufacture method of anode of lithium ion secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102207021A CN102723462A (en) | 2012-06-29 | 2012-06-29 | Manufacture method of anode of lithium ion secondary battery |
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| CN2012102207021A Pending CN102723462A (en) | 2012-06-29 | 2012-06-29 | Manufacture method of anode of lithium ion secondary battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199258A (en) * | 2013-03-07 | 2013-07-10 | 中航锂电（洛阳）有限公司 | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery |
| CN103579615A (en) * | 2013-08-19 | 2014-02-12 | 惠州亿纬锂能股份有限公司 | Anode material of lithium battery and lithium battery using anode material |
| CN104766945A (en) * | 2015-03-30 | 2015-07-08 | 深圳市斯盛能源股份有限公司 | Lithium ion secondary battery positive pole piece and production method thereof |
| CN105580165A (en) * | 2013-07-24 | 2016-05-11 | 日产自动车株式会社 | Non-aqueous electrolyte secondary battery positive electrode and non-aqueous electrolyte secondary battery using same |
| CN106663777A (en) * | 2014-07-24 | 2017-05-10 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery |
| CN112952050A (en) * | 2019-12-11 | 2021-06-11 | 广州汽车集团股份有限公司 | Positive active material, positive pole piece, lithium ion soft package battery cell, lithium ion battery pack and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199258A (en) * | 2013-03-07 | 2013-07-10 | 中航锂电（洛阳）有限公司 | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery |
| CN103199258B (en) * | 2013-03-07 | 2016-06-22 | 中航锂电（江苏）有限公司 | Anode material for lithium-ion batteries, anode preparation method and lithium ion battery |
| CN105580165A (en) * | 2013-07-24 | 2016-05-11 | 日产自动车株式会社 | Non-aqueous electrolyte secondary battery positive electrode and non-aqueous electrolyte secondary battery using same |
| CN105580165B (en) * | 2013-07-24 | 2018-08-14 | 日产自动车株式会社 | Positive electrode for nonaqueous electrolyte secondary battery and the non-aqueous electrolyte secondary battery for having used the anode |
| CN103579615A (en) * | 2013-08-19 | 2014-02-12 | 惠州亿纬锂能股份有限公司 | Anode material of lithium battery and lithium battery using anode material |
| CN106663777A (en) * | 2014-07-24 | 2017-05-10 | 丰田自动车株式会社 | Nonaqueous electrolyte secondary battery |
| CN104766945A (en) * | 2015-03-30 | 2015-07-08 | 深圳市斯盛能源股份有限公司 | Lithium ion secondary battery positive pole piece and production method thereof |
| CN112952050A (en) * | 2019-12-11 | 2021-06-11 | 广州汽车集团股份有限公司 | Positive active material, positive pole piece, lithium ion soft package battery cell, lithium ion battery pack and application thereof |
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Application publication date: 20121010 |
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