CN102299366A - Lithium ion battery of lithium titanate and lithium manganate system and preparation method thereof - Google Patents
Lithium ion battery of lithium titanate and lithium manganate system and preparation method thereof Download PDFInfo
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- CN102299366A CN102299366A CN2011102177267A CN201110217726A CN102299366A CN 102299366 A CN102299366 A CN 102299366A CN 2011102177267 A CN2011102177267 A CN 2011102177267A CN 201110217726 A CN201110217726 A CN 201110217726A CN 102299366 A CN102299366 A CN 102299366A
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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 invention discloses a lithium ion battery of a lithium titanate and lithium manganate system; the cathode material comprises 85-95% by weight of lithium manganate, 1-10% by weight of adhesives, and 3-10% by weight of conductive agents; the anode material comprises 85-95% by weight of lithium titanate (Li4Ti5O12), 1-10% by weight of adhesives, and 2-10% by weight of conductive agents. The lithium ion power battery of the invention has a large capacity, excellent rate charge and discharge, a long cycle life, and high stability and safety performance, is applicable to fields of hybrid electric vehicles, rapid-charging distance-increasing pure electric public traffic systems, large-scale energy-storage systems, domestic energy-storage power stations, military products with high performance requirements, and the like. The invention also discloses a preparation method of the lithium ion power battery; the method adopts aqueous adhesives such as 103 glue, 103A glue, 105 glue, LA132, and the like for binding, adopts water as a solvent, has low cost, simple and practical process, has no environmental pollution, and is environment-friendly and energy-saving.
Description
Technical field
The present invention relates to a kind of lithium ion battery and preparation method thereof, be specifically related to a kind of lithium titanate and LiMn2O4 system lithium ion battery and preparation method thereof.
Background technology
Traditional lithium ion battery as the negative material main raw material(s), has stable performance, the higher characteristics of specific energy with graphite.Yet graphite also has self intrinsic defective: as overtension easy " analysing lithium ", cause fail safe hidden danger.The diaphragm that negative material surface forms, in recycling process since continual chemical reaction and crystal formation change, also at the cyclicity and the electrical property that constantly influence battery.And finally cause decreased performance and cell decay.
Lithium titanate is a kind of novel ion secondary battery negative material, has excellent cycle performance and good charge and discharge platform.Deformation own is little owing to discharging and recharging is called as " zero strain material ", has greatly improved the cycle performance and the security performance of battery itself, is called a kind of material that " thoroughly " solves battery safety in the industry.
But the electrode potential of lithium titanate own is higher, and the cell voltage of being made as negative pole by it is lower, therefore will select the positive electrode coupling of high potential.The lithium manganate material electrode potential is higher, and cost is lower, is desirable lithium titanate cell positive material.
In the slurry of electrode was made, using maximum adhesives was PVDF, and a kind of fluoropolymer, its solvent are NMP(n-formyl sarcolysine base pyrrolidones).Raw material, PVDF, conductive agent etc. are mixed by a certain percentage, after the process high-speed stirred is prepared into slurry, be applied to equably on the aluminium foil, through oven dry, roll, cut into pole piece then, finish the electrode manufacturing at painting process.NMP is an organic solvent, has the strong impulse smell, 203 ℃ of boiling points, 95 ℃ of flash-points, explosion limit 1.3%-9.5%.NMP distributes strong smell in air, contaminated environment must be reclaimed, and directly manufacturing has increased cost to battery.And NMP must distribute in coater oven, air channel in time, otherwise security incident such as can blast, catch fire.NMP is an organic solvent, has certain corrosivity.And NMP-PVDF solvent suction can influence the adhesiveness of PVDF, needs strictly to control moisture in the electrode manufacturing, thus the manufacture difficulty and the cost of increase.
Thereby, in the development process of lithium-ion-power cell, select a kind of suitable aqueous binder, use water as solvent, for solving the problems of the technologies described above, have great importance.
Summary of the invention
The object of the present invention is to provide a kind of negative pole with the lithium titanate be primary raw material, anodal be main raw material(s) with the LiMn2O4, carry out with aqueous binder bonding, with water as lithium-ion-power cell of solvent and preparation method thereof.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of lithium titanate and LiMn2O4 system lithium ion battery, its positive electrode is made up of the LiMn2O4 of 85 ~ 95% weight, the adhesive of 1 ~ 10% weight, the conductive agent of 3 ~ 10% weight; Its negative material is by the lithium titanate (Li of 85 ~ 95% weight
4Ti
5O
12), the conductive agent of the adhesive of 1 ~ 10% weight, 2 ~ 10% weight forms; Described adhesive is an aqueous binder.
Preferably, described aqueous binder is a polyether compound.
Preferably, described aqueous binder is at least a among 103 glue, 103A glue, 105 glue, the LA132.
Preferably, described conductive agent is at least a in SP, superconduction carbon black, electrically conductive graphite, the carbon nano-tube.
The preparation method of above-mentioned a kind of lithium titanate and LiMn2O4 system lithium ion battery comprises the steps:
1) making of positive plate: press formula ratio and add positive electrode, be dissolved in water, stir, anode sizing agent, anode sizing agent is coated on the aluminium foil, under vacuum environment, 80-120 ℃ of baking be after 5-12 hour, roll-in, cuts into positive plate;
2) making of negative plate: press formula ratio and add negative material, be dissolved in water, stir, cathode size, cathode size is coated on the aluminium foil, under vacuum environment, 80-120 ℃ of baking be after 5-12 hour, roll-in, cuts into negative plate;
3) respectively with positive plate, negative plate under vacuum environment, 60 ~ 120 ℃ the baking 12 ~ 24 hours after, positive plate, barrier film, negative plate are laminated into electric core together, insert in the battery container, become the semi-finished product battery;
4) with the semi-finished product battery under vacuum environment, 60 ~ 90 ℃ the baking 48 ~ 96 hours after, fluid injection, change into, partial volume, obtain a kind of lithium titanate and LiMn2O4 system lithium ion battery.
Preferably, the vacuum pressure of described vacuum environment is-0.08 ~-0.10 MPa.
The present invention has following beneficial effect:
(1) adopts lower-cost LiMn2O4 as positive electrode, reduced battery cost;
(2) lithium-ion-power cell of the present invention used polyether compound as 103 glue, 103A glue, 105 glue, LA132 as adhesive, bond effect is good, in addition, this class adhesive is an aqueous binder, can make water as solvent, thereby has avoided shortcomings such as organic solvent is inflammable and explosive, perishable, contaminated environment, and the processing cost of water is low, to zero environmental, greatly reduce the manufacture difficulty and the cost of battery, environmental protection and energy saving;
(3) low, simple for process, the non-environmental-pollution of manufacture method cost of the present invention, the lithium-ion-power cell capacity for preparing according to the method is big, rate charge-discharge is good, have extended cycle life, stability and safety performance height, energy-conserving and environment-protective can be applicable to the fields such as military products of hybrid-electric car, quick charge range-extended electric public transit system, large-scale energy-storage system, family's energy-accumulating power station, high performance requirements.
Description of drawings
Fig. 1 is the charge graph of the lithium-ion-power cell of the embodiment of the invention 1;
Fig. 2 is the discharge curve of the lithium-ion-power cell of the embodiment of the invention 1;
Fig. 3 is the charge graph of the lithium-ion-power cell of the embodiment of the invention 2;
Fig. 4 is the discharge curve of the lithium-ion-power cell of the embodiment of the invention 2;
Fig. 5 is the charge graph of the lithium-ion-power cell of the embodiment of the invention 3;
Fig. 6 is the discharge curve of the lithium-ion-power cell of the embodiment of the invention 3.
Embodiment
A kind of lithium titanate and LiMn2O4 system lithium ion battery, its positive electrode is made up of the LiMn2O4 of 85 ~ 95% weight, the adhesive of 1 ~ 10% weight, the conductive agent of 3 ~ 10% weight; Its negative material is by the lithium titanate (Li of 85 ~ 95% weight
4Ti
5O
12), the conductive agent of the adhesive of 1 ~ 10% weight, 2 ~ 10% weight forms; Described adhesive is an aqueous binder.
Preferably, described aqueous binder is a polyether compound.
Preferably, described aqueous binder is at least a among 103 glue, 103A glue, 105 glue, the LA132.Certainly, in those skilled in the art's understanding scope, can also select other polyether compound aqueous binder for use.
Preferably, described conductive agent is at least a in SP, superconduction carbon black, electrically conductive graphite, the carbon nano-tube.Certainly, in those skilled in the art's understanding scope, can also select other conductive agent for use.
The preparation method of above-mentioned a kind of lithium titanate and LiMn2O4 system lithium ion battery comprises the steps:
1) making of positive plate: press formula ratio and add positive electrode, be dissolved in water, stir, anode sizing agent, anode sizing agent is coated on the aluminium foil, under vacuum environment, 80-120 ℃ of baking be after 5-12 hour, roll-in, cuts into positive plate;
2) making of negative plate: press formula ratio and add negative material, be dissolved in water, stir, cathode size, cathode size is coated on the aluminium foil, under vacuum environment, 80-120 ℃ of baking be after 5-12 hour, roll-in, cuts into negative plate;
3) respectively with positive plate, negative plate under vacuum environment, 60 ~ 120 ℃ the baking 12 ~ 24 hours after, positive plate, barrier film, negative plate are laminated into electric core together, insert in the battery container, become the semi-finished product battery;
4) with the semi-finished product battery under vacuum environment, 60 ~ 90 ℃ the baking 48 ~ 96 hours after, fluid injection, change into, partial volume, obtain a kind of lithium titanate and LiMn2O4 system lithium ion battery.
Preferably, the vacuum pressure of described vacuum environment is-0.08 ~-0.10 MPa.
The present invention is further illustrated below in conjunction with embodiment, but be not limited thereto.
Embodiment 1
A kind of lithium titanate and LiMn2O4 system lithium ion battery comprise positive pole, negative pole, barrier film, electrolyte and shell.
Positive electrode is formed: 85% LiMn2O4,5% 103 glue, 10% SP;
Negative material is formed: 85% lithium titanate, 5% LA132,10% SP;
Barrier film is: the single-layer septum of PP material;
Electrolyte is: 1.2mol/L LiPF
6Solution, solvent composition are EC:DMC:EMC=1:1:1;
Shell is a plastic casing.
Concrete preparation method is as follows:
1) making of positive plate: press formula ratio and add positive electrode, be dissolved in water, even with double star power mixer high-speed stirred, eliminate bubble, iron filings, anode sizing agent, anode sizing agent is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under-0.08MPa, 100 ℃ of bakings roll-in, cut into positive plate after 10 hours;
2) making of negative plate: press formula ratio and add negative material, be dissolved in water, even with double star power mixer high-speed stirred, eliminate bubble, iron filings, cathode size, cathode size is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under-0.08MPa, 100 ℃ of bakings roll-in, cut into negative plate after 10 hours;
3) respectively the 110 ℃ of bakings under-0.08MPa of positive plate, negative plate are laminated into electric core together with positive plate, barrier film, negative plate after 24 hours, insert in the plastic casing, become the semi-finished product battery;
4) with the semi-finished product battery in 80 ℃ of bakings under the-0.08MPa after 72 hours, fluid injection, change into, partial volume becomes the 130Ah battery.After tested, the charging and discharging curve of gained battery as shown in Figure 1 and Figure 2.
A kind of lithium titanate and LiMn2O4 system lithium ion battery comprise positive pole, negative pole, barrier film, electrolyte and shell.
Positive electrode is formed: 90% LiMn2O4,7% 103A glue, 3% superconduction carbon black;
Negative material is formed: 85% lithium titanate, 10% LA132,5% superconduction carbon black;
Barrier film is: the single-layer septum of PP material;
Electrolyte is: 1.2mol/L LiPF
6Solution, solvent composition are EC:DMC:EMC=1:1:1;
Shell is a plastic casing.
Concrete preparation method:
1) making of positive plate: press formula ratio and add positive electrode, be dissolved in water, even with double star power mixer high-speed stirred, eliminate bubble, iron filings, anode sizing agent, anode sizing agent is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under-0.09MPa, 80 ℃ of bakings roll-in, cut into positive plate after 12 hours;
2) making of negative plate: press formula ratio and add negative material, be dissolved in water, even with double star power mixer high-speed stirred, eliminate bubble, iron filings, cathode size, cathode size is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under-0.09MPa, 80 ℃ of bakings roll-in, cut into negative plate after 12 hours;
3) respectively the 100 ℃ of bakings under-0.09MPa of positive plate, negative plate are laminated into electric core together with positive plate, barrier film, negative plate after 12 hours, insert in the plastic casing, become the semi-finished product battery;
4) with the semi-finished product battery in 80 ℃ of bakings under the-0.09MPa after 48 hours, fluid injection, change into, partial volume becomes the 130Ah battery.After tested, the charging voltage of gained battery is 2.7v, and discharge voltage is 1.5v, and the battery charging and discharging curve as shown in Figure 3, Figure 4.
Embodiment 3
A kind of lithium titanate and LiMn2O4 system lithium ion battery comprise positive pole, negative pole, barrier film, electrolyte and shell.
Positive electrode is formed: 95% LiMn2O4,1% 103 glue, 103A glue mixture, 4% carbon nano-tube;
Negative material is formed: 95% lithium titanate, 1% 105 glue, 4% carbon nano-tube;
Barrier film is: the single-layer septum of PP material;
Electrolyte is: 1.2mol/L LiPF
6Solution, solvent composition are EC:DMC:EMC=1:1:1;
Shell is a plastic casing.
Concrete preparation method is:
1) making of positive plate: press formula ratio and add positive electrode, be dissolved in water, even with double star power mixer high-speed stirred, eliminate bubble, iron filings, anode sizing agent, anode sizing agent is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under-0.10MPa, 120 ℃ of bakings roll-in, cut into positive plate after 5 hours;
2) making of negative plate: press formula ratio and add negative material, be dissolved in water, even with double star power mixer high-speed stirred, eliminate bubble, iron filings, cathode size, cathode size is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under-0.10MPa, 120 ℃ of bakings roll-in, cut into negative plate after 5 hours;
3) respectively the 110 ℃ of bakings under-0.10MPa of positive plate, negative plate are laminated into electric core together with positive plate, barrier film, negative plate after 36 hours, insert in the plastic casing, become the semi-finished product battery;
4) with the semi-finished product battery in 80 ℃ of bakings under the-0.10MPa after 60 hours, fluid injection, change into, partial volume becomes the 130Ah battery.After tested, the charging voltage of gained battery is 2.7v, and discharge voltage is 1.5v, battery charging and discharging curve such as Fig. 5, shown in Figure 6.
Claims (6)
1. lithium titanate and LiMn2O4 system lithium ion battery, its positive electrode is made up of the LiMn2O4 of 85 ~ 95% weight, the adhesive of 1 ~ 10% weight, the conductive agent of 3 ~ 10% weight; Its negative material is by the lithium titanate (Li of 85 ~ 95% weight
4Ti
5O
12), the conductive agent of the adhesive of 1 ~ 10% weight, 2 ~ 10% weight forms; Described adhesive is an aqueous binder.
2. a kind of lithium titanate according to claim 1 and LiMn2O4 system lithium ion battery is characterized in that: described aqueous binder is a polyether compound.
3. a kind of lithium titanate according to claim 2 and LiMn2O4 system lithium ion battery is characterized in that: described aqueous binder is at least a among 103 glue, 103A glue, 105 glue, the LA132.
4. a kind of lithium titanate according to claim 1 and LiMn2O4 system lithium ion battery is characterized in that: described conductive agent is at least a in SP, superconduction carbon black, electrically conductive graphite, the carbon nano-tube.
5. the preparation method of described a kind of lithium titanate of claim 1 and LiMn2O4 system lithium ion battery comprises the steps:
1) making of positive plate: press formula ratio and add positive electrode, be dissolved in water, stir, anode sizing agent, anode sizing agent is coated on the aluminium foil, under vacuum environment, 80-120 ℃ of baking be after 5-12 hour, roll-in, cuts into positive plate;
2) making of negative plate: press formula ratio and add negative material, be dissolved in water, stir, cathode size, cathode size is coated on the aluminium foil, under vacuum environment, 80-120 ℃ of baking be after 5-12 hour, roll-in, cuts into negative plate;
3) respectively with positive plate, negative plate under vacuum environment, 60 ~ 120 ℃ the baking 12 ~ 24 hours after, positive plate, barrier film, negative plate are laminated into electric core together, insert in the battery container, become the semi-finished product battery;
4) with the semi-finished product battery under vacuum environment, 60 ~ 90 ℃ the baking 48 ~ 96 hours after, fluid injection, change into, partial volume, obtain a kind of lithium titanate and LiMn2O4 system lithium ion battery.
6. according to the preparation method of described a kind of lithium titanate of claim 5 and LiMn2O4 system lithium ion battery, it is characterized in that: the vacuum pressure of described vacuum environment is-0.08 ~-0.10 MPa.
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Cited By (3)
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| CN102324551A (en) * | 2011-08-01 | 2012-01-18 | 珠海锂源动力科技有限公司 | Lithium titanate and lithium manganese lithium ion battery and preparation method thereof |
| CN103456963A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation methods of silicon-graphene composite material and lithium ion battery |
| CN105762353A (en) * | 2016-04-08 | 2016-07-13 | 远东福斯特新能源有限公司 | Lithium-ion battery with high-nickel ternary aqueous positive electrode and preparation method thereof |
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| CN102324551A (en) * | 2011-08-01 | 2012-01-18 | 珠海锂源动力科技有限公司 | Lithium titanate and lithium manganese lithium ion battery and preparation method thereof |
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| CN105762353A (en) * | 2016-04-08 | 2016-07-13 | 远东福斯特新能源有限公司 | Lithium-ion battery with high-nickel ternary aqueous positive electrode and preparation method thereof |
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