CN102299371A - Lithium ion power cell and preparation method of lithium ion power cell - Google Patents

Lithium ion power cell and preparation method of lithium ion power cell Download PDF

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CN102299371A
CN102299371A CN2011102310297A CN201110231029A CN102299371A CN 102299371 A CN102299371 A CN 102299371A CN 2011102310297 A CN2011102310297 A CN 2011102310297A CN 201110231029 A CN201110231029 A CN 201110231029A CN 102299371 A CN102299371 A CN 102299371A
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lithium
power cell
ion
lithium ion
vacuum environment
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CN102299371B (en
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李宝玉
王保
刘兴福
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ZHUHAI LIYUAN NEW ENERGY TECHNOLOGY Co Ltd
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
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Abstract

The invention discloses a lithium ion power cell and a preparation method of the lithium ion power cell. A negative material is made from the following raw materials of: by weight, 83-94% of lithium titanate, 2-10% of an adhesive and 3-10% of a conductive agent; a positive material is made from the following raw materials of: by weight, 82-93% of lithium manganate, 1-10% of the adhesive and 4-12% of the conductive agent. The lithium ion power cell provided by the invention has advantages of low cost, large capacity, long cycle life and good safety performance, and can be applied in many fields, such as hybrid electric vehicles, military goods with high property requirements and the like. The preparation method provided by the invention is simple. As water is used as a solvent instead of using NMP as the solvent during the electrode manufacturing process, there exists no pollution as well as dangerous accidents such as explosion or combustion, the zero discharge of pollutants is realized, and simultaneously the complexity of the cell processing technology is reduced.

Description

The preparation method of a kind of lithium-ion-power cell and lithium-ion-power cell
Technical field
The present invention relates to the preparation method of a kind of lithium-ion-power cell and lithium-ion-power cell.
Background technology
World energy sources and environmental protection situation day are becoming tight, and battery more and more is subjected to people's favor as new forms of energy.Lithium ion battery is owing to its energy density height, and volume is light, and weight is little, and is environment friendly and pollution-free, becomes the main direction of new forms of energy development.Fast development along with electric automobile, space technology, national defense industry and electric power energy-storage system etc., had higher requirement in aspects such as the specific capacity of secondary cell, cycle life, fail safe, improve and the chemical property that improves battery can be started with from aspects such as electrode materials.
Traditional lithium ion battery invariably with graphite as the negative material main active substances.With graphite as the prescription of negative electrode active material comparative maturity.Graphite is the lithium-ion battery system of negative pole, and self intrinsic defective is also arranged.As overtension easy " analysing lithium ", cause fail safe hidden danger, present commercial lithium ion battery negative material all is embedding lithium material with carbon element mostly.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.Simultaneously, also there is the common imbedding problem of electrolyte in graphite electrode, and this also will influence the cyclical stability of electrode.
Lithium titanate anode material is the lithium titanate with spinel structure superfines, is the lithium secondary battery cathode material of a kind of high-performance, high magnification type.LTO is 1.55V with respect to the current potential of lithium electrode, and theoretical specific capacity is 175mAh/g, actual specific capacity 150-160 mAh/g, and concentrate on land regions, have excellent cycle performance and good charge and discharge platform.Embed or deviate from the process at Li, crystal formation does not change, change in volume is less than 1%, therefore be called as " zero strain material ", this is significant, can avoid in the charge and discharge cycles owing to the flexible back and forth of electrode material causes structural damage, thus the cycle performance and the useful life of improving electrode, having reduced with the cycle-index increase and brought specific capacity significantly to decay, is (Li 4Ti 5O 12) have than carbon negative pole good cycle performance more.There is not electrolyte imbedding problem altogether in lithium titanate, can not influence cycle life owing to the instability of SEI.Lithium titanate anode material has stable physics and chemical property, with the electrolyte reaction, does not have outstanding stability in use and fail safe.Under 25 ℃, Li 4Ti 5O 12The chemical diffusion coefficient be 2 * 10 -8Cm 2/ s makes a call to an order of magnitude than the diffusion coefficient in the carbon negative pole material, and high diffusion coefficient makes that this negative material can quick, many cycle charge-discharges.The lithium titanate material electromotive force is difficult for producing the lithium dendrite arm than the height of pure metal lithium, for the safety that ensures lithium battery provides the foundation.Be considered to thoroughly to solve the fail safe of lithium battery.
Positive electrode also is an important component part of lithium-ion-power cell, and the positive electrode by the Sony industrialization has mainly adopted cobalt acid lithium (LiCoO at first 2), and now because cobalt resource is more and more deficienter, its price is also more and more higher, its thermal stability is relatively poor simultaneously, environment also there is bigger destruction, therefore, increasing researcher and engineering staff have turned one's attention to other positive electrode, and the positive electrode that lithium-ion-power cell receives much concern also has LiNiO 2, LiMn 2O 4, LiFePO4 etc., LiNiO 2Capacity is bigger, and the comparison difficulty but preparation is got up obtain purer material and be difficult to, and its security performance is bad; LiMn 2O 4Price is relatively cheap, and security performance is also better, yet its cycle performance is relatively poor, and capacity is not high, and high-temperature behavior is not good simultaneously, LiFePO 4Do not contain noble element, raw material cheapness, resource are greatly abundant, yet, with LiFePO 4For the voltage of the battery of positive active material lower.
The current potential of LiMn2O4 is higher, and LiMn2O4 has overall merits such as price is low, current potential is high, environmental friendliness, security performance height simultaneously, is subjected to increasing people and pays close attention to.
When making electrode slurry, adhesive commonly used is PVDF, and solvent commonly used is NMP, yet use the problem of NMP to be: environmental pollution is big, and NMP belongs to inflammable and explosive article, in the process of making electrode slurry, should be noted that in time ventilates NMP to distribute removes, in addition, because NMP can absorb water, and then influences the bond properties of adhesive, therefore, in the process of making electrode, must control the moisture content of NMP, therefore, it is complicated that technology can become.
Summary of the invention
The purpose of this invention is to provide a kind of lithium-ion-power cell and preparation method thereof.
The technical solution used in the present invention is:
A kind of lithium-ion-power cell, negative material is made up of the raw material of following mass percent: the conductive agent of the lithium titanate of 83-94%, the adhesive of 2-10%, 3-10%, positive electrode is made up of the raw material of following mass percent: the conductive agent of the LiMn2O4 of 82-93%, the adhesive of 1-10%, 4-12%.
Described adhesive is at least a among LA132, LA133, the LA135.
Described conductive agent is at least a in SP, superconduction carbon black, electrically conductive graphite, the carbon nano-tube.
A kind of preparation method of lithium-ion-power cell 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-ion-power cell.
The vacuum pressure of described vacuum environment is-0.08 ~-0.10 MPa.
The invention has the beneficial effects as follows: lithium-ion-power cell cost 1. of the present invention is lower, and capacity is bigger, has extended cycle life, and security performance is good, can be applicable to a lot of fields, as hybrid-electric car, and the militaria of high performance requirements etc.; 2. manufacture method of the present invention is simple; 3. owing to do not use NMP in making the process of electrode, and water is cooked solvent, therefore, can not produce pollution, perils such as blast or burning also can not occur, and zero emission has reduced the cell production process complexity simultaneously.
Description of drawings
Fig. 1 is the discharge curve of lithium-ion-power cell of the present invention.
Fig. 2 is the charging curve of lithium-ion-power cell of the present invention.
Fig. 3 is the discharge curve of lithium-ion-power cell of the present invention.
Fig. 4 is the charging curve of lithium-ion-power cell of the present invention.
Fig. 5 is the cyclic curve figure of lithium-ion-power cell of the present invention.
Embodiment
Further specify the present invention below in conjunction with specific embodiment:
Embodiment 1:
A kind of prescription of lithium ion power cell cathode pole piece material table 1 composed as follows:
Figure 2011102310297100002DEST_PATH_IMAGE001
A kind of prescription of lithium ion power battery cathode pole piece material table 2 composed as follows:
Figure 2011102310297100002DEST_PATH_IMAGE002
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, get anode sizing agent, anode sizing agent is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 80 ℃ of bakings after 12 hours, roll-in, cuts into positive plate;
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, get cathode size, cathode size is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 80 ℃ of bakings after 12 hours, roll-in, cuts into negative plate;
3) respectively the 60 ℃ 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 60 ℃ of bakings under the-0.08MPa after 96 hours, fluid injection, change into, partial volume becomes the 120Ah battery.After tested, the 0.5C discharge curve of gained battery as shown in Figure 1, the 0.5C charging curve is as shown in Figure 2.
Embodiment 2:
A kind of prescription of lithium ion power cell cathode pole piece material table 3 composed as follows:
Figure 2011102310297100002DEST_PATH_IMAGE003
A kind of prescription of lithium ion power battery cathode pole piece material table 4 composed as follows:
Figure 2011102310297100002DEST_PATH_IMAGE004
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, get anode sizing agent, anode sizing agent is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 100 ℃ of bakings after 10 hours, roll-in, cuts into positive plate;
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, get cathode size, cathode size is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 100 ℃ of bakings after 10 hours, roll-in, cuts into negative plate;
3) respectively the 120 ℃ of bakings under-0.10MPa 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 90 ℃ of bakings under the-0.10MPa after 48 hours, fluid injection, change into, partial volume becomes the 120Ah battery.After tested, the 0.5C discharge curve of gained battery as shown in Figure 3, the 0.5C charging curve is as shown in Figure 4.
Embodiment 3:
A kind of prescription of lithium ion power cell cathode pole piece material table 5 composed as follows:
Figure 2011102310297100002DEST_PATH_IMAGE005
A kind of prescription of lithium ion power battery cathode pole piece material table 6 composed as follows:
Figure 2011102310297100002DEST_PATH_IMAGE006
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, get anode sizing agent, anode sizing agent is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 120 ℃ of bakings after 5 hours, roll-in, cuts into positive plate;
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, get cathode size, cathode size is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 120 ℃ of bakings after 5 hours, roll-in, cuts into negative plate;
3) respectively the 120 ℃ of bakings under-0.10MPa 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 90 ℃ of bakings under the-0.10MPa after 48 hours, fluid injection, change into, partial volume becomes the 120Ah battery.The 1C cyclic curve of gained battery as shown in Figure 5.
Embodiment 4:
A kind of prescription of lithium ion power cell cathode pole piece material table 7 composed as follows:
Figure 2011102310297100002DEST_PATH_IMAGE007
A kind of prescription of lithium ion power battery cathode pole piece material table 8 composed as follows:
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, get anode sizing agent, anode sizing agent is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 120 ℃ of bakings after 5 hours, roll-in, cuts into positive plate;
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, get cathode size, cathode size is uniformly coated on the aluminium foil through automatical feeding system, coating machine, under vacuum environment, 120 ℃ of bakings after 5 hours, roll-in, cuts into negative plate;
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 16 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 72 hours, fluid injection, change into, partial volume becomes the 120Ah battery.

Claims (5)

1. lithium-ion-power cell, it is characterized in that: negative material is made up of the raw material of following mass percent: the conductive agent of the lithium titanate of 83-94%, the adhesive of 2-10%, 3-10%, positive electrode is made up of the raw material of following mass percent: the conductive agent of the LiMn2O4 of 82-93%, the adhesive of 1-10%, 4-12%.
2. a kind of lithium-ion-power cell according to claim 1 is characterized in that: described adhesive is at least a among LA132, LA133, the LA135.
3. a kind of cathode material of lithium-ion power battery according to claim 1 is characterized in that: described conductive agent is at least a in SP, superconduction carbon black, electrically conductive graphite, the carbon nano-tube.
4. the preparation method of the described a kind of lithium-ion-power cell of claim 1 is characterized in that: comprise 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-ion-power cell.
5. the preparation method of a kind of lithium-ion-power cell according to claim 4, it is characterized in that: the vacuum pressure of described vacuum environment is-0.08 ~-0.10 MPa.
CN201110231029.7A 2011-08-12 2011-08-12 Lithium ion power cell and preparation method of lithium ion power cell Expired - Fee Related CN102299371B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101222045A (en) * 2007-12-27 2008-07-16 南京工业大学 Method for synthesizing nano-scale lithium ion power cell cathode material by micro-reactor self-ignition method
CN101582522A (en) * 2009-06-23 2009-11-18 珠海市鹏辉电池有限公司 High rate charge-discharge power lithium battery
CN101958428A (en) * 2010-09-15 2011-01-26 东莞新能源科技有限公司 Lithium ion secondary battery
CN101964428A (en) * 2010-08-05 2011-02-02 深圳市贝特瑞新能源材料股份有限公司 Preparation method of lamellar lithium manganese battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101222045A (en) * 2007-12-27 2008-07-16 南京工业大学 Method for synthesizing nano-scale lithium ion power cell cathode material by micro-reactor self-ignition method
CN101582522A (en) * 2009-06-23 2009-11-18 珠海市鹏辉电池有限公司 High rate charge-discharge power lithium battery
CN101964428A (en) * 2010-08-05 2011-02-02 深圳市贝特瑞新能源材料股份有限公司 Preparation method of lamellar lithium manganese battery
CN101958428A (en) * 2010-09-15 2011-01-26 东莞新能源科技有限公司 Lithium ion secondary battery

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