CN101630728A - High energy density lithium secondary battery electrode and preparation method thereof - Google Patents
High energy density lithium secondary battery electrode and preparation method thereof Download PDFInfo
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- CN101630728A CN101630728A CN200910061624A CN200910061624A CN101630728A CN 101630728 A CN101630728 A CN 101630728A CN 200910061624 A CN200910061624 A CN 200910061624A CN 200910061624 A CN200910061624 A CN 200910061624A CN 101630728 A CN101630728 A CN 101630728A
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Abstract
The invention discloses a high energy density lithium secondary battery electrode and a preparation method thereof. The electrode consists of current collector and active material layers adhered on the current collector. The active material layer is made from lithium-storage active material and conductive polymer material, and the mass ratio of the lithium-storage active material and the conductive polymer material is 100:0.1-40. In the invention, the conductive polymer material is adopted as main conductive agent and adhesive, compared with the conductive agent and adhesive of the traditional electrode, the electrode in the invention has high energy density due to that the conductive polymer material can provide a certain amount of reversible capacity for batteries by electrochemical doping and undoping reaction.
Description
Technical field
The present invention relates to electrochemistry, materials chemistry and chemical power source product technical field, be specifically related to a kind of lithium secondary battery electrode and preparation method thereof.
Background technology
Along with the increasingly extensive application of lithium secondary battery in portable electronic fields such as mobile phone, laptop computer, gamma cameras, the advantage of its high voltage that shows, high-energy-density and long circulation life has attracted the favor of military affairs, space flight, the contour technical applications of electric automobile.No matter be the low-power applications field for portable type electronic product, still to high-power applications occasions such as electric automobiles, the energy density that further improves battery is one of most important target of pursuing of lithium secondary battery all the time.
Basically, energy content of battery density depends on electrode material, but the influence of battery preparation technique also can not be ignored.Such as for based on LiCoO
218650 type lithium ion batteries of/graphite material system, the 1Ah of its discharge capacity before about 10 years brought up to 2.2 present～2.5Ah, the corresponding battery specific energy is from 110～120Wh/kg, 210Wh/L brought up to 190～200Wh/kg and＞500Wh/L, huge advance made on these energy densities mainly is by improving the preparation technology of battery, obtaining such as the compacted density of improving design, raising electrode active material and minimizing negative pole residual capacity etc.This shows,, improve effect that technology for preparing electrode obtains sometimes and not second to selecting new material system for use for the energy density that improves battery.
Study by improving the lithium secondary battery energy density from people in recent years, overwhelming majority work all concentrates on the electrode material aspect, such as coating (coat as carbon, nano metal is or/and the nano-metal-oxide coating) and element doping by the surface (as LiFePO
4Li position, Fe position, P position, O position mix) improve the electronic conductance and the ionic conductance of material, by reducing the particle diameter of material, preparation sub-micron or nano material are to reduce the diffusion length of lithium ion, these measures can improve the utilance of active material, thereby improve the actual specific energy of battery.Aspect the preparation technology of electrode, then lack innovation for many years,, improve the conductivity of electrode, satisfy the needs of machine-shaping by adding bonding agents such as PVDF, PTFE by adding conductive agents such as carbon black, acetylene black still based on traditional preparation method.Because these traditional conductive agents and bonding agent all belong to electrochemically inactive material, their adding must reduce the relative amount of electrochemical active material in electrode, and this has reduced the actual specific energy of battery on sizable degree.
Summary of the invention
The object of the present invention is to provide an analogy traditional electrode to have lithium secondary battery electrode of high-energy-density more and preparation method thereof.
A kind of high energy density lithium secondary battery electrode, constitute by collector and the active material layer that is bonded on the collector, it is characterized in that: described active material layer is made up of storage lithium active material and conducting polymer composite, and the mass ratio of storage lithium active material and conducting polymer composite is 100: 0.1～40.
Described storage lithium active material is cobalt acid lithium LiCoO
2, lithium nickelate LiNiO
2, LiMn2O4 LiMn
2O
4, trielement composite material LiCo
xNi
yMn
zO
2, wherein x+y+z=1, LiFePO4 LiFePO
4, in graphite, MCMB, metallic tin, tinbase composite material, elemental silicon and the silicon alloy any one, perhaps above-mentioned any one material is carried out element doping or the surface coats resulting composite material.
Described conducting polymer composite is polypyrrole PPy or polyaniline PANI or polythiophene PTh or poly-derivative to benzene PPP or poly-phenylene vinylene (ppv) PPV or above-mentioned any one conducting polymer composite.
As improvement, described active material layer also contains conductive auxiliary agent and bonding auxiliary agent, and conductive auxiliary agent and bonding auxiliary agent account for 0～30% and 0～10% of whole active material layer quality respectively.
Described conductive auxiliary agent is any one or the combination in carbon-based conductive agent, graphite based conducting agent, Metal Substrate conductive agent and the metallic compound conductive agent.
Described bonding auxiliary agent is any one or the combination in polytetrafluoroethylene, Kynoar, butadiene-styrene rubber, sodium carboxymethylcellulose, polyurethane, polyvinyl alcohol, the Viton.
The preparation method of above-mentioned lithium secondary battery electrode is specially: conductive high polymer monomer is dissolved in makes conductive high polymer monomer solution in the good solvent, add storage lithium active material powder and supporting electrolyte in this solution, stir and obtain suspension-turbid liquid; Placing this suspension-turbid liquid with collector with to electrode, is that work electrode carries out the electrochemical polymerization reaction with the collector, obtains lithium secondary battery electrode.
As improvement, also in described conductive high polymer monomer solution, add conductive auxiliary agent.
As further improvement, also in described conductive high polymer monomer solution, add bonding auxiliary agent.
Technique effect of the present invention is embodied in:
(1) the present invention adopts conducting polymer composite to prepare electrode, because conducting polymer has the conductivity of metal and the cementability of polymer concurrently, can play the effect of conductive agent and bonding agent simultaneously, thereby this electrode can not use or use more on a small quantity the bonding agent and the conductive agent of electrochemistry inertia, conducting polymer also has certain electro-chemical activity by the reaction of doping and dedoping simultaneously, and this all helps improving the actual specific energy of battery.
(2) characteristic of the easy film forming of conducting polymer composite make its with storage lithium active material and collector between have good the contact, greatly improved the electron conduction of electrode, help improving the high power discharge ability of battery.
(3) pliability of conducting polymer composite makes electrode can bear the influence that pole piece expands and contraction is impacted in the large current density electric process, has the longer life-span.
In sum, this electrode with conducting polymer replacement conventional adhesive and conductive agent is suitable for high-energy-density, and is high-power, the lithium secondary battery of long circulation life.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples can only be used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area makes some nonessential improvement and adjusts according to the content of the invention described above and still belongs to protection scope of the present invention.
Comparative Examples 1 84: 12: 4 by mass percentage is with carbon-coated LiFePO 4 for lithium ion batteries C-LiFePO
4, after acetylene black AB and polytetrafluoroethylene PTFE emulsion mix, be rolled into the film of thick about 100 μ m, be pressed in then on the stainless (steel) wire collector and form cell working electrode, be to electrode with metal lithium sheet, microporous polypropylene membrane is a barrier film, with 1mol/L LiPF
6/ EC-DMC (1: 1) solution is electrolyte assembling button cell and in the voltage range of 4.1～2.5V, and 0.1C discharges under the current density of 20C, and experimental result provides at table 1.This electrode specific discharge capacity under the 0.1C current density is 142mAh/g, and specific discharge capacity is 60mAh/g under the 5C current density, can not discharge substantially under the 20C current density.
Comparative Examples 2 90: 5: 5 by mass percentage is with lithium titanate Li
4Ti
5O
12, after carbon black CB and polytetrafluoroethylene PTFE emulsion mix, be rolled into the film of thick about 100 μ m, be pressed in then on the nickel foam collector and form cell working electrode, be to electrode with metal lithium sheet, microporous polypropylene membrane is a barrier film, with 1mol/L LiPF
6/ EC-DMC (1: 1) solution is electrolyte assembling button cell and in the voltage range of 0.2～2.5V, carries out the constant current charge-discharge experiment under the 0.2C current density, and the reversible specific capacity that records this electrode is about 147mAh/g.
Embodiment 1 at first prepares the acetonitrile solution of 100ml 0.1mol/L pyrroles Py, adds 1g carbon-coated LiFePO 4 for lithium ion batteries C-LiFePO
4Powder and 0.2g supporting electrolyte LiClO
4, ultrasonic concussion obtains uniform suspension-turbid liquid half an hour, then stainless (steel) wire is placed this suspension-turbid liquid as work electrode with to electrode, applies 0.1mA/cm on this work electrode
2Current density carry out the constant current electrochemical polymerization, polymerization obtains layer of even PPy and coats C-LiFePO on the work electrode after 1 hour
4Composite membrane, learn C-LiFePO by differential thermal analysis
4: PPy=84: 16, be anode directly with this work electrode, with the metal lithium sheet negative pole, microporous polypropylene membrane is a barrier film, with 1mol/L LiPF
6/ EC-DMC (1: 1) solution is electrolyte assembling button cell and in the voltage range of 4.1～2.5V, and 0.1C discharges under the current density of 20C, and experimental result provides in table 1.For the purpose of contrasting, traditional LiFePO4 electrode (C-LiFePO in the Comparative Examples 1
4: discharge curve AB: PTFE=75: 20: 5) also provides (the two used C-LiFePO in table
4Material is identical material).From table, can see C-LiFePO
4/ PPy electrode specific discharge capacity under the 0.1C current density is 158mAh/g, and specific discharge capacity is 111mAh/g under the 5C current density, and specific discharge capacity still can reach 87mAh/g under the 20C current density, far above traditional C-LiFePO
4Electrode demonstrates outstanding high-energy-density and large current discharging capability.
Table 1 charging and discharging capacity is contrast table as a result
Embodiment 2 at first prepares the acetonitrile solution of 100ml 0.01mol/L aniline, adds 2g lithium titanate Li then
4Ti
5O
12Powder, 0.5g supporting electrolyte LiPF
6, 0.02g conductive auxiliary agent carbon black CB and 0.02g conductive auxiliary agent graphite, the bonding auxiliary agent polytetrafluoroethylene PTFE of 0.01g, ultrasonic dispersion got uniform suspension-turbid liquid in 2 hours, then with nickel foam as work electrode, with electrode is placed this suspension-turbid liquid, potential region (with respect to the Ag/AgCl reference electrode) at 1.3V～0.1V carries out the cyclic voltammetric electrochemical polymerization, has reacted after 1.2 hours at the work electrode uniform deposition one deck polyaniline and has coated Li
4Ti
5O
12Film, learn Li by differential thermal analysis
4Ti
5O
12: PPy: PTFE: (CB+ graphite)=93: 2: 2: 3, be cell working electrode directly with this electrode, with the metal lithium sheet be battery to electrode, be barrier film with the microporous polypropylene membrane, with 1mol/L LiPF
6/ EC-DMC (1: 1) solution is electrolyte assembling button cell, and in the voltage range of 0.2～2.5V, carries out the constant current charge-discharge experiment under the 0.2C current density, and the reversible specific capacity that records this electrode is about 175mAh/g.Compare Li with Comparative Examples 2
4Ti
5O
12/ PANI electrode has high discharge capacity, thereby has high energy density.
Embodiment 3 at first prepares the acetonitrile solution of 100ml 0.2mol/L to benzene PP, adds 1gLiMn
2O
4Powder, 0.2g supporting electrolyte LiClO
4With the bonding auxiliary agent polytetrafluoroethylene PTFE of 0.1g, ultrasonic concussion obtained uniform suspension-turbid liquid in 1 hour, then with the aluminium net as work electrode, with electrode is placed this suspension-turbid liquid, the current potential that applies 1.2V (with respect to the Ag/AlCl reference electrode) on this work electrode carries out the constant potential electrochemical polymerization, obtains the layer of even polypyrrole after polymerase 10 .5 hour on the work electrode and coats LiMn
2O
4Composite membrane, learn LiMn by differential thermal analysis
2O
4: PPy: PTFE=70: directly with this work electrode be cell working electrode at 22: 8, and the lithium sheet is a negative pole, is barrier film with the microporous polypropylene membrane, with 1mol/L LiPF
6/ EC-DMC (1: 1) solution is electrolyte assembling button cell, voltage range at 4.3～2.5V, 2C carries out charge and discharge cycles under the current density of 20C, this electrode specific discharge capacity under the 2C current density can snap into about 130mAh/g, still can keep specific discharge capacity 95mAh/g under the 10C current density.
Claims (9)
1, a kind of high energy density lithium secondary battery electrode, constitute by collector and the active material layer that is bonded on the collector, it is characterized in that: described active material layer is made up of storage lithium active material and conducting polymer composite, and the mass ratio of storage lithium active material and conducting polymer composite is 100: 0.1～40.
2, lithium secondary battery electrode according to claim 1 is characterized in that: described storage lithium active material is cobalt acid lithium LiCoO
2, lithium nickelate LiNiO
2, LiMn2O4 LiMn
2O
4, trielement composite material LiCo
xNi
yMn
zO
2, wherein x+y+z=1, LiFePO4 LiFePO
4, in graphite, MCMB, metallic tin, tinbase composite material, elemental silicon and the silicon alloy any one, perhaps above-mentioned any one material is carried out element doping or the surface coats resulting composite material.
3, lithium secondary battery electrode according to claim 1 is characterized in that: described conducting polymer composite is polypyrrole PPy or polyaniline PANI or polythiophene PTh or poly-derivative to benzene PPP or poly-phenylene vinylene (ppv) PPV or above-mentioned any one conducting polymer composite.
4, lithium secondary battery electrode according to claim 1 is characterized in that, described active material layer also contains conductive auxiliary agent and bonding auxiliary agent, and conductive auxiliary agent and bonding auxiliary agent account for 0～30% and 0～10% of whole active material layer quality respectively.
5, lithium secondary battery electrode according to claim 4 is characterized in that: described conductive auxiliary agent is any one or the combination in carbon-based conductive agent, graphite based conducting agent, Metal Substrate conductive agent and the metallic compound conductive agent.
6, lithium secondary battery electrode according to claim 4 is characterized in that, described bonding auxiliary agent is any one or the combination in polytetrafluoroethylene, Kynoar, butadiene-styrene rubber, sodium carboxymethylcellulose, polyurethane, polyvinyl alcohol, the Viton.
7, the preparation method of the described lithium secondary battery electrode of claim 1, be specially: conductive high polymer monomer is dissolved in makes conductive high polymer monomer solution in the good solvent, add storage lithium active material powder and supporting electrolyte in this solution, ultrasonic wave disperses or stirs to obtain suspension-turbid liquid; Placing this suspension-turbid liquid with collector with to electrode, is that work electrode carries out the electrochemical polymerization reaction with the collector, obtains lithium secondary battery electrode.
8, preparation method according to claim 7 is characterized in that: also add conductive auxiliary agent in described conductive high polymer monomer solution.
9, according to claim 7 or 8 described preparation methods, it is characterized in that: also in described conductive high polymer monomer solution, add bonding auxiliary agent.
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| CN200910061624A CN101630728A (en) | 2009-04-16 | 2009-04-16 | High energy density lithium secondary battery electrode and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102487141A (en) * | 2010-12-02 | 2012-06-06 | 比亚迪股份有限公司 | Cathode material of lithium ion battery and battery |
| CN102522529A (en) * | 2011-12-30 | 2012-06-27 | 美美电池有限公司 | Manufacturing method for lead acid storage cell conductive polymer polar plate |
| CN102544432A (en) * | 2010-12-13 | 2012-07-04 | 依诺特生物能量控股公司 | Positive electrode and battery with same |
| CN104393299A (en) * | 2014-09-23 | 2015-03-04 | 西北师范大学 | Nanometer silicon-polythiophene electric conduction composite material for lithium ion battery, and preparation method thereof |
| CN104600314A (en) * | 2015-01-04 | 2015-05-06 | 合肥国轩高科动力能源股份公司 | Method for preparing lithium battery positive pole piece |
| CN106058151A (en) * | 2016-08-12 | 2016-10-26 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulfur/polyaniline composite electrode, and preparation method and application thereof |
| CN106784735A (en) * | 2017-02-06 | 2017-05-31 | 安徽鹰龙工业设计有限公司 | A kind of lithium battery composite positive pole and preparation method thereof |
| CN107210438A (en) * | 2015-09-14 | 2017-09-26 | 株式会社东芝 | Nonaqueous electrolyte battery and battery bag |
| CN108390093A (en) * | 2018-04-14 | 2018-08-10 | 齐鲁工业大学 | A kind of lithium battery of the positive electrode based on surface chemical modification |
| CN109103441A (en) * | 2018-09-10 | 2018-12-28 | 江苏塔菲尔新能源科技股份有限公司 | Modified composite material, preparation method and the purposes in lithium ion battery of siliceous substrates material |
| CN114649509A (en) * | 2022-04-07 | 2022-06-21 | 楚能新能源股份有限公司 | Method for preparing anode of lithium ion battery |
-
2009
- 2009-04-16 CN CN200910061624A patent/CN101630728A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102487141A (en) * | 2010-12-02 | 2012-06-06 | 比亚迪股份有限公司 | Cathode material of lithium ion battery and battery |
| CN102487141B (en) * | 2010-12-02 | 2014-08-13 | 比亚迪股份有限公司 | Cathode material of lithium ion battery and battery |
| CN102544432A (en) * | 2010-12-13 | 2012-07-04 | 依诺特生物能量控股公司 | Positive electrode and battery with same |
| CN102522529A (en) * | 2011-12-30 | 2012-06-27 | 美美电池有限公司 | Manufacturing method for lead acid storage cell conductive polymer polar plate |
| CN102522529B (en) * | 2011-12-30 | 2014-09-17 | 美美电池有限公司 | Manufacturing method for lead acid storage cell conductive polymer polar plate |
| CN104393299A (en) * | 2014-09-23 | 2015-03-04 | 西北师范大学 | Nanometer silicon-polythiophene electric conduction composite material for lithium ion battery, and preparation method thereof |
| CN104600314A (en) * | 2015-01-04 | 2015-05-06 | 合肥国轩高科动力能源股份公司 | Method for preparing lithium battery positive pole piece |
| CN104600314B (en) * | 2015-01-04 | 2017-05-03 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium battery positive pole piece |
| CN107210438A (en) * | 2015-09-14 | 2017-09-26 | 株式会社东芝 | Nonaqueous electrolyte battery and battery bag |
| CN106058151A (en) * | 2016-08-12 | 2016-10-26 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulfur/polyaniline composite electrode, and preparation method and application thereof |
| CN106784735A (en) * | 2017-02-06 | 2017-05-31 | 安徽鹰龙工业设计有限公司 | A kind of lithium battery composite positive pole and preparation method thereof |
| CN108390093A (en) * | 2018-04-14 | 2018-08-10 | 齐鲁工业大学 | A kind of lithium battery of the positive electrode based on surface chemical modification |
| CN109103441A (en) * | 2018-09-10 | 2018-12-28 | 江苏塔菲尔新能源科技股份有限公司 | Modified composite material, preparation method and the purposes in lithium ion battery of siliceous substrates material |
| CN114649509A (en) * | 2022-04-07 | 2022-06-21 | 楚能新能源股份有限公司 | Method for preparing anode of lithium ion battery |
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