CN104466098A - Ionic-liquid-coated lithium ion battery positive plate as well as preparation method thereof and lithium ion battery - Google Patents
Ionic-liquid-coated lithium ion battery positive plate as well as preparation method thereof and lithium ion battery Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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Abstract
The invention discloses an ionic-liquid-coated lithium ion battery positive plate as well as a preparation method thereof and a lithium ion battery. The ionic-liquid-coated lithium ion battery positive plate comprises a positive active material, a conductive agent, a positive binder, an ionic liquid, a solvent and a positive current collector. Compared with the prior art, the prepared lithium ion battery positive electrode has the advantages of high specific energy and specific capacity, and good safety, so that the defects of low specific energy, an unstable material structure, poor cycle performance and low oxide positive electrode material safety of the existing lithium ion battery positive plate material are overcome, and therefore, a positive electrode material with high safety, high specific energy and low cost is provided for the lithium ion battery. The preparation method of the ionic-liquid-coated lithium ion battery positive plate is simple in process, low in production cost and suitable for large-scale industrial production.
Description
Technical field
The invention belongs to chemical cell technical field, be specifically related to coated based lithium-ion battery positive plate of a kind of ionic liquid and preparation method thereof, a kind of lithium ion battery.
Background technology
Lithium ion battery gains great popularity because of advantages such as its voltage are high, energy density is high, have extended cycle life, environmental pollution is little, but along with the fast development of electronic information technology, it is also proposed higher requirement to the performance of lithium ion battery.In recent years, the improvement of Carbon anode performance and electrolytical selection all had made great progress.Comparatively speaking, the research of anode material for lithium-ion batteries is comparatively delayed, becomes the key factor that restriction lithium ion battery overall performance improves further.Therefore, the research of positive electrode is just being subject to increasing attention.
At present, the main positive electrode in domestic market is cobalt acid lithium, lithium nickelate, LiMn2O4, and LiFePO4, lithium manganese phosphate, phosphoric acid vanadium lithium, lithium nickel cobalt dioxide, nickel-cobalt-manganese ternary material.Cobalt acid lithium (LiCoO
2) preparation technology is simple, charging/discharging voltage is higher, and cycle performance is excellent and obtain extensive use; But because cobalt resource is rare, cost is higher, environmental pollution is comparatively large and anti-over-charging ability is poor, its development space is restricted.Lithium nickelate (LiNiO
2) specific capacity is comparatively large, but easily generate product, structural stability and the poor heat stability of non-stoichiometric during preparation.LiMn2O4 is except the LiMn of spinel structure
2o
4outward, the LiMnO of layer structure is also had
2, its laminate LiMnO
2specific capacity is comparatively large, but it belongs to thermodynamics metastable state, structural instability, there is Jahn-Teller effect and cycle performance is poor, spinel structure LiMn
2o
4technique is simple, and cheap, charging/discharging voltage is high, environmentally friendly, and security performance is excellent, but specific capacity is lower, and under high temperature, capacity attenuation is more serious.LiFePO4 belongs to newer positive electrode, and its fail safe is high, cost is lower, but has that discharge voltage low (3.4V), tap density are low, the not yet deficiency such as batch production.Nickel-cobalt-manganese ternary compound is substantially identical with cobalt acid lithium structure.This material has merged the advantage of cobalt acid lithium, lithium nickelate and LiMn2O4, and specific discharge capacity is high, and thermal stability is better than cobalt acid lithium, and cycle performance is better, price is relatively low, and development in recent years rapidly, and is used widely.
Ionic liquid is made up of anions and canons completely, organic substance liquid under uniform temperature, it has wider electrochemical window, almost there is no vapour pressure, wider thermal stable temperature scope, chemical stability advantages of higher, the electrolyte as lithium secondary battery uses the fail safe that can significantly improve battery.
Though have been reported now, ionic liquid is used as electrolyte, but ionic liquid viscosity is too high and price is higher, is used as lithium-ion battery electrolytes consumption large, causes cost too high, cannot commercialization.And lithium ion battery ionic liquid being used for clad anode does not appear in the newspapers.
Summary of the invention
For solving the problems of the technologies described above, based lithium-ion battery positive plate that the object of the present invention is to provide a kind of ionic liquid coated and preparation method thereof.Preparation just have specific energy and specific capacity is high, fail safe is good advantage.
Present invention also offers a kind of lithium ion battery.
The based lithium-ion battery positive plate that a kind of ionic liquid provided by the invention is coated, comprising: positive electrode active materials, conductive agent, positive electrode binder, ionic liquid, solvent and plus plate current-collecting body;
Wherein, the weight of described positive electrode active materials, conductive agent, positive electrode binder and ionic liquid is:
The weight of solvent for use is the 50-200% of the total weight of positive electrode active materials, conductive agent, positive electrode binder and ionic liquid;
Described positive electrode active materials is LiFePO4, cobalt acid lithium, LiMn2O4, lithium nickelate, lithium manganese phosphate, phosphoric acid vanadium lithium, one of lithium nickel cobalt dioxide or nickel-cobalt-manganese ternary material; Conductive agent is acetylene black, one of carbon black or graphite or combination in any; Positive electrode binder is one of polytetrafluoroethylene or Kynoar; Ionic liquid is ion liquid of quaternaries or glyoxaline ion liquid or pyridine ionic liquid or one of piperidines ionic liquid or pyrrole ionic liquid; Solvent is one of 1-METHYLPYRROLIDONE, dimethylformamide or two kinds.
Described plus plate current-collecting body adopts aluminium foil, and aluminum foil thickness is 0.015-0.020mm;
The preparation method of the based lithium-ion battery positive plate that a kind of ionic liquid provided by the invention is coated, comprises the following steps:
By the positive electrode binder of the conductive agent of the positive electrode active materials of 50-90 part, 4-20 part, 5-20 part, the ionic liquid of 1-10 part and account for positive electrode active materials, conductive agent, positive electrode binder become anode sizing agent with the solvent of the 50-200% of the total weight of ionic liquid, plus plate current-collecting body adopts two-sided blade coating, baking vacuumizes, after drying, after roll-in, form positive plate.
A kind of lithium ion battery provided by the invention, comprising: lithium ion cell positive, negative pole, barrier film and electrolyte that shell, ionic liquid are coated.
The cathode size that described negative pole is become by negative active core-shell material, thickener, negative electrode binder, solvent and negative current collector form;
The weight of described negative active core-shell material, thickener, negative electrode binder is:
Negative active core-shell material 83-95 part
Thickener 2-7 part
Negative electrode binder 3-10 part;
The weight of solvent for use is the 60-120% of negative active core-shell material, thickener, negative electrode binder total weight.
Described negative material is one or both in graphite, polymer charcoal, and thickener is CMC, and negative electrode binder is one in LA132, LA133, SBR butadiene-styrene rubber or combination in any, and solvent is water, and described negative current collector adopts Copper Foil.
The preparation method of described negative pole, comprises the following steps:
By the thickener of the negative active core-shell material of 83-95 part, 2-7 part, the negative electrode binder of 3-10 part and account for negative active core-shell material, thickener, negative electrode binder total weight the solvent of 60-120% become cathode size, be coated on negative current collector, baking vacuumizes, after drying, after roll-in, form negative pole.
The present invention uses ionic liquid clad anode to have following advantage: ionic liquid has high solubility, can increase dispersiveness in anode sizing agent manufacturing process; Ionic liquid is coated on positive electrode surface, has blocked active material and has contacted with the direct of electrolyte the corrosion caused, improve the stability of battery, thus fail safe has been higher; Ionic liquid is dense in surface of active material, defines conducting film, reduces internal resistance, improves the conductivity of positive pole; Positive electrode is combined with ionic liquid, changes the original structure of positive electrode, improves the specific capacity of battery; Adopt ionic liquid clad anode material, ionic liquid consumption is few, and electrolyte uses conventional electrolysis liquid, reduces cost.
Compare with prior art, lithium ion battery prepared by the present invention has following beneficial effect: the advantage that lithium ion cell positive has specific energy and specific capacity is high, fail safe is good, overcome existing anode material for lithium-ion batteries specific energy low, material structure is unstable, cycle performance is poor, and the shortcoming that oxide anode material fail safe is not high, thus provide the positive electrode of high security, high-energy-density, low cost for lithium-ion-power cell.Preparation method's technique of the present invention is simple, and production cost is low, is applicable to large-scale industrial production.
Embodiment
For better the object, technical solutions and advantages of the present invention being described, by specific embodiment, the invention will be further described below.
Embodiment 1
The based lithium-ion battery positive plate that ionic liquid is coated, comprising: LiFePO4 85 parts, acetylene black 6 parts, Kynoar 8 parts, ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate 1 part and solvent N-methyl pyrilidone 100 parts.
A preparation method for the based lithium-ion battery positive plate that ionic liquid is coated, comprises the following steps:
By LiFePO4 85 parts, acetylene black 6 parts, Kynoar 8 parts, ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate 1 part, mixed grinding, oven dry, then add solvent N-methyl pyrilidone 100 parts to stir, make anode sizing agent, slurry is coated on the two sides of aluminium foil, after 110 DEG C of dryings, roll-in, obtains positive plate.
A kind of lithium ion battery, its preparation process is:
By 92.5 parts, graphite, CMC 3.5 parts, negative electrode binder LA1324 part, deionized water 80 parts, makes cathode size, cathode size is evenly coated on the two sides of Copper Foil, and after 110 DEG C of dryings, roll-in, obtains negative plate.By the above-mentioned positive plate that prepared and the isolation of negative plate PP composite membrane, inject electrolyte, electrolyte is LiPF
6carbonic acid diformazan vinegar, propylene carbonate vinegar, its mass ratio is 1:1, obtains battery after sealing, battery first discharge specific capacity 148.6mAh/g, the ferric phosphate lithium cell first discharge specific capacity 130.1mAh/g not adding ionic liquid obtained in the same way, modified specific capacity improves 14.2%.
Embodiment 2
The based lithium-ion battery positive plate that ionic liquid is coated, comprising: cobalt acid lithium 83.8 parts, acetylene black 7 parts, polytetrafluoroethylene 8 parts, ionic liquid 1-butyl-3-methyl imidazolium fluoroform sulphonate 1.2 parts and solvent dimethylformamide 100 parts.
A preparation method for the based lithium-ion battery positive plate that ionic liquid is coated, comprises the following steps:
Cobalt acid lithium 83.8 parts, acetylene black 7 parts, polytetrafluoroethylene 8 parts, ionic liquid 1-butyl-3-methyl imidazolium fluoroform sulphonate 1.2 parts of mixed grindings, oven dry, then add solvent dimethylformamide 100 parts to stir, make anode sizing agent, slurry is coated on the two sides of aluminium foil, after 110 DEG C of dryings, roll-in, obtains positive plate.
A kind of lithium ion battery, its preparation process is:
By 87 parts, graphite, CMC 6.5 parts, negative electrode binder LA1336.5 part, deionized water 110 parts, makes cathode size, cathode size is evenly coated on the two sides of Copper Foil.After 110 DEG C of dryings, roll-in, obtains negative plate.By the above-mentioned positive plate that prepared and the isolation of negative plate PP composite membrane, inject electrolyte, electrolyte is LiPF6 carbonic acid diformazan vinegar, propylene carbonate vinegar, its mass ratio is 1:1, battery is obtained after sealing, battery first discharge specific capacity 139.5mAh/g, the un-added cobalt acid lithium battery first discharge specific capacity 124.8mAh/g obtained in the same way, modified specific capacity improves 18.2%.
Embodiment 3
The based lithium-ion battery positive plate that ionic liquid is coated, comprising: LiMn2O4 82.5 parts, acetylene black 7 parts, Kynoar 9 parts, ionic liquid N-butyl-pyridinium tetrafluoroborate 1.5 parts and solvent dimethylformamide 90 parts.
A preparation method for the based lithium-ion battery positive plate that ionic liquid is coated, comprises the following steps:
By LiMn2O4 82.5 parts, acetylene black 7 parts, Kynoar 9 parts, ionic liquid N-butyl-pyridinium tetrafluoroborate 1.5 parts, mixed grinding, oven dry, then add solvent dimethylformamide 90% to stir, make anode sizing agent, slurry is coated on the two sides of aluminium foil, after 110 DEG C of dryings, roll-in, obtains positive plate.
A kind of lithium ion battery, its preparation process is:
By 88 parts, graphite, CMC 6.5 parts, negative electrode binder SBR 5.5 parts, deionized water 90 parts, makes cathode size, cathode size is evenly coated on the two sides of Copper Foil.After 110 DEG C of dryings, roll-in, obtains negative plate.By the above-mentioned positive plate that prepared and the isolation of negative plate PP composite membrane, inject electrolyte, electrolyte is LiPF
6carbonic acid diformazan vinegar, propylene carbonate vinegar, its mass ratio is 1:1, obtains battery after sealing, battery first discharge specific capacity 128.7mAh/g, the un-added lithium manganate battery first discharge specific capacity 110.8Ah/g obtained in the same way, modified specific capacity improves 16.2%.
Embodiment 4
The based lithium-ion battery positive plate that ionic liquid is coated, comprising: lithium nickelate 80 parts, conductive agent acetylene black 9 parts, positive electrode binder Kynoar 10 parts, ionic liquid tetramethyl-ammonium tetrafluoroborate 1 part and dimethylformamide 100 parts.
A preparation method for the based lithium-ion battery positive plate that ionic liquid is coated, comprises the following steps:
By lithium nickelate 80 parts, conductive agent acetylene black 9 parts, positive electrode binder Kynoar 10 parts, ionic liquid tetramethyl-ammonium tetrafluoroborate 1 part, mixed grinding, oven dry, then add solvent dimethylformamide 100 parts to stir, make anode sizing agent, slurry is coated on the two sides of aluminium foil, after 110 DEG C of dryings, roll-in, obtains positive plate.
A kind of lithium ion battery, its preparation process is:
By 85 parts, graphite, CMC 6 parts, negative electrode binder SBR 9 parts, deionized water 100 parts, makes cathode size, cathode size is evenly coated on the two sides of Copper Foil.After 110 DEG C of dryings, roll-in, obtains negative plate.By the above-mentioned positive plate that prepared and the isolation of negative plate PP composite membrane, inject electrolyte, electrolyte is LiPF
6carbonic acid diformazan vinegar, propylene carbonate vinegar, its mass ratio is 1:1, obtains battery after sealing, battery first discharge specific capacity 176.9mAh/g, the un-added lithium nickelate battery first discharge specific capacity 150.6mAh/g obtained in the same way, modified specific capacity improves 17.5%.
Embodiment 5
The based lithium-ion battery positive plate that ionic liquid is coated, comprising: nickel-cobalt-manganese ternary material 80 parts, conductive agent acetylene black 10 parts, positive electrode binder Kynoar 8 parts, ionic liquid N-butyl-N-methyl piperidine bromine salt 2 parts and dimethylformamide 120 parts.
A preparation method for the based lithium-ion battery positive plate that ionic liquid is coated, comprises the following steps:
By nickel-cobalt-manganese ternary material 80 parts, conductive agent acetylene black 10 parts, positive electrode binder Kynoar 8 parts, ionic liquid N-butyl-N-methyl piperidine bromine salt 2 parts of mixed grindings, oven dry, then add solvent dimethylformamide 120 parts to stir, make anode sizing agent.Slurry is coated on the two sides of aluminium foil, after 110 DEG C of dryings, roll-in, obtains positive plate.
A kind of lithium ion battery, its preparation process is:
86 parts, graphite, CMC 6 parts, negative electrode binder SBR 8 parts, deionized water 120 parts, makes cathode size, cathode size is evenly coated on the two sides of Copper Foil.After 110 DEG C of dryings, roll-in, obtains negative plate.By the above-mentioned positive plate that prepared and the isolation of negative plate PP composite membrane, inject electrolyte, electrolyte is LiPF6 carbonic acid diformazan vinegar, propylene carbonate vinegar, its mass ratio is 1:1, battery is obtained after sealing, battery first discharge specific capacity 203.2mAh/g, the un-added nickel cobalt manganese cell first discharge specific capacity 175.2mAh/g obtained in the same way, modified specific capacity improves 16.0%.
The effect that above-described embodiment just produces the lithium ion battery Ingredients Weight difference of ionic liquid clad anode is done one and is compared; do not limit practical range of the present invention; all employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop in protection scope of the present invention.
Claims (9)
1. the based lithium-ion battery positive plate that ionic liquid is coated, is characterized in that, the coated based lithium-ion battery positive plate of described ionic liquid comprises: positive electrode active materials, conductive agent, positive electrode binder, ionic liquid, solvent and plus plate current-collecting body.
2. the based lithium-ion battery positive plate that ionic liquid according to claim 1 is coated, is characterized in that, the weight of described positive electrode active materials, conductive agent, positive electrode binder and ionic liquid is:
The weight of solvent for use is the 50-200% of the total weight of positive electrode active materials, conductive agent, positive electrode binder and ionic liquid.
3. the based lithium-ion battery positive plate that ionic liquid according to claim 1 and 2 is coated, it is characterized in that, described ionic liquid is ion liquid of quaternaries or glyoxaline ion liquid or pyridine ionic liquid or one of piperidines ionic liquid or pyrrole ionic liquid.
4. the based lithium-ion battery positive plate that ionic liquid according to claim 3 is coated, it is characterized in that, described positive electrode active materials is LiFePO4, cobalt acid lithium, LiMn2O4, lithium nickelate, lithium manganese phosphate, phosphoric acid vanadium lithium, one of lithium nickel cobalt dioxide or nickel-cobalt-manganese ternary material.
5. the based lithium-ion battery positive plate that ionic liquid according to claim 4 is coated, is characterized in that, described conductive agent is acetylene black, one of carbon black or graphite or combination in any.
6. the based lithium-ion battery positive plate that ionic liquid according to claim 5 is coated, is characterized in that, described positive electrode binder is one of polytetrafluoroethylene or Kynoar.
7. the based lithium-ion battery positive plate that ionic liquid according to claim 6 is coated, is characterized in that, described solvent is one of 1-METHYLPYRROLIDONE, dimethylformamide or two kinds.
8. a preparation method for the based lithium-ion battery positive plate that the ionic liquid described in any one of claim 1-7 is coated, is characterized in that, described preparation method comprises the following steps:
Just the conductive agent of the positive electrode active materials of 50-90 part, 4-20 part, the positive electrode binder of 5-20 part, the ionic liquid of 1-10 part and account for positive electrode active materials, conductive agent, positive electrode binder become anode sizing agent with the solvent of the 50-200% of the total weight of ionic liquid, plus plate current-collecting body adopts two-sided blade coating, baking vacuumizes, after drying, after roll-in, form positive plate.
9. a lithium ion battery, is characterized in that, described lithium ion battery comprises: based lithium-ion battery positive plate, negative pole, barrier film and electrolyte that shell, ionic liquid are coated.
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| CN105489897A (en) * | 2015-11-27 | 2016-04-13 | 中航锂电（洛阳）有限公司 | Conductive liquid for lithium ion battery ternary positive electrode material and preparation method for conductive liquid, and lithium ion battery |
| CN105914340A (en) * | 2016-06-22 | 2016-08-31 | 宁德新能源科技有限公司 | Positive pole plate, fabrication method thereof and lithium ion battery containing pole plate |
| CN106252649A (en) * | 2016-10-11 | 2016-12-21 | 宁德新能源科技有限公司 | A kind of anode pole piece and the lithium ion battery containing this pole piece |
| CN107093716A (en) * | 2017-04-15 | 2017-08-25 | 三峡大学 | A kind of preparation method of ion liquid modified high-performance vanadium phosphate sodium/carbon composite anode material |
| CN109004230A (en) * | 2018-08-09 | 2018-12-14 | 芜湖彰鸿工程技术有限公司 | A kind of lithium ion battery anode glue size and preparation method thereof |
| CN110061207A (en) * | 2019-03-29 | 2019-07-26 | 中国人民解放军国防科技大学 | Nickel-cobalt-aluminum ternary cathode material coated with chelate copolymer gel layer and preparation method and application thereof |
| CN110265743A (en) * | 2019-06-24 | 2019-09-20 | 中国科学院过程工程研究所 | A kind of ionic liquid coats the regeneration method of waste and old power battery artificial graphite material |
| CN111675248A (en) * | 2020-06-10 | 2020-09-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of mesoporous ternary nanosheet cathode material, product and application thereof |
| CN112820937A (en) * | 2019-11-15 | 2021-05-18 | 郑州宇通集团有限公司 | Solid electrolyte, preparation method thereof and high-nickel ternary all-solid-state battery |
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| CN105489897A (en) * | 2015-11-27 | 2016-04-13 | 中航锂电（洛阳）有限公司 | Conductive liquid for lithium ion battery ternary positive electrode material and preparation method for conductive liquid, and lithium ion battery |
| CN105489897B (en) * | 2015-11-27 | 2018-05-04 | 中航锂电（洛阳）有限公司 | Ternary cathode material of lithium ion battery conduction liquid and preparation method thereof, lithium ion battery |
| CN105914340B (en) * | 2016-06-22 | 2019-05-24 | 宁德新能源科技有限公司 | A kind of anode pole piece, preparation method and the lithium ion battery containing the pole piece |
| CN105914340A (en) * | 2016-06-22 | 2016-08-31 | 宁德新能源科技有限公司 | Positive pole plate, fabrication method thereof and lithium ion battery containing pole plate |
| CN106252649A (en) * | 2016-10-11 | 2016-12-21 | 宁德新能源科技有限公司 | A kind of anode pole piece and the lithium ion battery containing this pole piece |
| CN107093716A (en) * | 2017-04-15 | 2017-08-25 | 三峡大学 | A kind of preparation method of ion liquid modified high-performance vanadium phosphate sodium/carbon composite anode material |
| CN109004230A (en) * | 2018-08-09 | 2018-12-14 | 芜湖彰鸿工程技术有限公司 | A kind of lithium ion battery anode glue size and preparation method thereof |
| CN109004230B (en) * | 2018-08-09 | 2020-11-20 | 义乌市君胜科技有限公司 | Lithium ion battery anode slurry and preparation method thereof |
| CN110061207A (en) * | 2019-03-29 | 2019-07-26 | 中国人民解放军国防科技大学 | Nickel-cobalt-aluminum ternary cathode material coated with chelate copolymer gel layer and preparation method and application thereof |
| CN110265743A (en) * | 2019-06-24 | 2019-09-20 | 中国科学院过程工程研究所 | A kind of ionic liquid coats the regeneration method of waste and old power battery artificial graphite material |
| CN110265743B (en) * | 2019-06-24 | 2021-11-09 | 中国科学院过程工程研究所 | Regeneration method of ionic liquid coated waste power battery artificial graphite material |
| CN112820937A (en) * | 2019-11-15 | 2021-05-18 | 郑州宇通集团有限公司 | Solid electrolyte, preparation method thereof and high-nickel ternary all-solid-state battery |
| CN111675248A (en) * | 2020-06-10 | 2020-09-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of mesoporous ternary nanosheet cathode material, product and application thereof |
| CN111675248B (en) * | 2020-06-10 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of mesoporous ternary nanosheet cathode material, product and application thereof |
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