CN102299374B - Lithium ion power battery and preparation method for lithium ion power battery - Google Patents
Lithium ion power battery and preparation method for lithium ion power battery Download PDFInfo
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- CN102299374B CN102299374B CN201110231042.2A CN201110231042A CN102299374B CN 102299374 B CN102299374 B CN 102299374B CN 201110231042 A CN201110231042 A CN 201110231042A CN 102299374 B CN102299374 B CN 102299374B
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Abstract
The invention discloses a lithium ion power battery and a preparation method for the lithium ion power battery. A negative electrode plate consists of the following ingredients in mass percent: 83 to 94 percent of lithium titanate, 2 to 10 percent of binding agents and 3 to 10 percent of conducting agents. A positive electrode material consists of the following ingredients in mass percent: 82 to 93 percent of lithium iron phosphate, 1 to 10 percent of binding agents and 3 to 11 percent of conducting agents. When the negative electrode plate or the positive electrode plate is manufactured, nmethylpyrrolidone (NMP) and polyvinylidene fluoride (PVDF) with pollution do not need to be used, energy saving and environment protection are realized in the manufacturing process, the cost is low, and the prepared lithium ion power battery has high safety performance and long circulation service.
Description
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 is more and more subject to people's favor as new forms of energy.Lithium ion battery is because its energy density is high, and volume is light, and weight is little, environment friendly and pollution-free, becomes the main direction of new forms of energy development.Along with the fast development of electric automobile, space technology, national defense industry and electric energy storing system etc., having higher requirement in the aspects such as specific capacity to secondary cell, cycle life, fail safe, improves the chemical property of battery and can start with from aspects such as electrode materials.
Traditional lithium ion battery is invariably using graphite as negative material main active substances.Comparative maturity of formula using graphite as negative electrode active material.Graphite is the lithium-ion battery system of negative pole, also has self intrinsic defect.As easily " analysing lithium " of overtension, cause fail safe hidden danger, current commercial lithium ion battery negative material is all embedding lithium material with carbon element mostly.The diaphragm that negative material surface forms, recycling in process because continual chemical reaction and crystal formation change, also at the cyclicity and the electrical property that constantly affect battery.And finally cause hydraulic performance decline and cell decay.Meanwhile, also there is the common imbedding problem of electrolyte in graphite electrode, and this also will affect the cyclical stability of electrode.
Lithium titanate anode material is 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, there is good cycle performance and good charge and discharge platform.At Li, embed or deviate from process, 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 charge and discharge cycles because the flexible back and forth of electrode material causes structural damage, thus cycle performance and the useful life of improving electrode, having reduced with cycle-index and increased and bring specific capacity significantly to decay, is (Li
4ti
5o
12) there is the cycle performance better than carbon negative pole.There is not electrolyte imbedding problem altogether in lithium titanate, can be due to the unstable cycle life that affects of SEI.Lithium titanate anode material has stable physics and chemistry character, does not react with electrolyte, has outstanding stability in use and fail safe.At 25 ℃, Li
4ti
5o
12chemical diffusion coefficient be 2 × 10
-8cm
2/ s, makes a call to an order of magnitude than the diffusion coefficient in carbon negative pole material, and high diffusion coefficient makes this negative material can quick, many cycle charge-discharges.Lithium titanate material electromotive force, than the height of pure metal lithium, is difficult for producing lithium dendrite arm, for the safety that ensures lithium battery provides the foundation.Be considered to thoroughly to solve the fail safe of lithium battery.
Positive electrode is also an important component part of lithium-ion-power cell, has mainly adopted cobalt acid lithium (LiCoO at first by the positive electrode of Sony industrialization
2), and now because cobalt resource is more and more deficienter, its price is also more and more higher, its thermal stability is poor simultaneously, environment is also had to larger 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, LiFePO
4deng, LiNiO
2capacity is larger, more difficult but preparation is got up, and 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, but its cycle performance is poor, and capacity is not high, and high-temperature behavior is not good simultaneously, LiFePO
4not containing noble element, raw material cheapness, resource is greatly abundant; Operating voltage is moderate, and voltage is more steady, and theoretical capacity is large, Stability Analysis of Structures, and security performance is also good.
While making electrode slurry, conventional adhesive is PVDF, and conventional solvent is NMP, but, use the problem of NMP to be: environmental pollution is large, and NMP belongs to inflammable and explosive article, making in the process of electrode slurry, should be noted that in time NMP ventilation is distributed and removed, in addition, because NMP can absorb water, and then affect the bond properties of adhesive, therefore, in the process of making electrode, must control the moisture content of NMP, therefore, it is complicated that technique can become.
Summary of the invention
The object 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 comprised 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 comprised of the raw material of following mass percent: the conductive agent of the LiFePO 4 of 82-93%, the adhesive of 1-10%, 3-11%.
Described adhesive is at least one in LA132, LA133, LA135.
Described conductive agent is at least one in SP, superconduction carbon black, electrically conductive graphite, carbon nano-tube.
A preparation method for lithium-ion-power cell, comprises the following steps:
1) making of positive plate: add positive electrode by formula ratio, be dissolved in water, stir, obtain anode sizing agent, anode sizing agent is coated on aluminium foil, under vacuum environment, 80-120 ℃ of baking, after 5-12 hour, roll-in, cuts into positive plate;
2) making of negative plate: add negative material by formula ratio, be dissolved in water, stir, obtain cathode size, cathode size is coated on aluminium foil, under vacuum environment, 80-120 ℃ of baking, after 5-12 hour, roll-in, cuts into negative plate;
3) respectively by positive plate, negative plate under vacuum environment, 60 ~ 120 ℃ baking 12 ~ 24 hours after, positive plate, barrier film, negative plate are laminated into battery core together, insert in battery container, become semi-finished product battery;
4) by semi-finished product battery under vacuum environment, 60 ~ 90 ℃ 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: 1. battery cost is lower, the lithium-ion-power cell capacity that the present invention obtains is larger, 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 not using NMP making in the process of electrode, and water is cooked solvent, therefore, can not produce pollution, also there will not be the perils such as blast or burning, and zero emission has reduced the complex manufacturing technology degree of battery simultaneously.
Accompanying drawing explanation
Fig. 1 is the charge graph of lithium-ion-power cell of the present invention.
Fig. 2 is the cyclic curve figure of lithium-ion-power cell of the present invention.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention:
embodiment 1:
A kind of formula table 1 composed as follows of lithium ion power cell cathode pole piece material:
A kind of formula table 2 composed as follows of lithium ion power battery cathode pole piece material:
Barrier film is: the single-layer septum of PP material
Electrolyte is: 1.2mol/L LiPF
6solution, solvent composition is EC:DMC:EMC=1:1:1
Shell is plastic casing
Concrete preparation method is as follows:
1) making of positive plate: add positive electrode by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain anode sizing agent, anode sizing agent is uniformly coated on 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: add negative material by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain cathode size, cathode size is uniformly coated on 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, after 24 hours, are laminated into battery core together by positive plate, barrier film, negative plate, insert in plastic casing, become semi-finished product battery;
4) by the 60 ℃ of bakings after 96 hours under-0.08MPa of semi-finished product battery, fluid injection, change into, partial volume becomes 120Ah battery.After tested, the 0.5C charging curve of gained battery as shown in Figure 1.
embodiment 2:
A kind of formula table 3 composed as follows of lithium ion power cell cathode pole piece material:
A kind of formula table 4 composed as follows of lithium ion power battery cathode pole piece material:
Barrier film is: the single-layer septum of PP material
Electrolyte is: 1.2mol/L LiPF
6solution, solvent composition is EC:DMC:EMC=1:1:1
Shell is plastic casing
Concrete preparation method is as follows:
1) making of positive plate: add positive electrode by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain anode sizing agent, anode sizing agent is uniformly coated on 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: add negative material by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain cathode size, cathode size is uniformly coated on 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, after 12 hours, are laminated into battery core together by positive plate, barrier film, negative plate, insert in plastic casing, become semi-finished product battery;
4) by the 90 ℃ of bakings after 48 hours under-0.10MPa of semi-finished product battery, fluid injection, change into, partial volume becomes 120Ah battery.After tested, the 1C cyclic curve of gained battery as shown in Figure 2.
embodiment 3:
A kind of formula table 5 composed as follows of lithium ion power cell cathode pole piece material:
A kind of formula table 6 composed as follows of lithium ion power battery cathode pole piece material:
Barrier film is: the single-layer septum of PP material
Electrolyte is: 1.2mol/L LiPF
6solution, solvent composition is EC:DMC:EMC=1:1:1
Shell is plastic casing
Concrete preparation method is as follows:
1) making of positive plate: add positive electrode by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain anode sizing agent, anode sizing agent is uniformly coated on 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: add negative material by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain cathode size, cathode size is uniformly coated on 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, after 12 hours, are laminated into battery core together by positive plate, barrier film, negative plate, insert in plastic casing, become semi-finished product battery;
4) by the 90 ℃ of bakings after 48 hours under-0.10MPa of semi-finished product battery, fluid injection, change into, partial volume becomes 120Ah battery.
embodiment 4:
A kind of formula table 7 composed as follows of lithium ion power cell cathode pole piece material:
A kind of formula table 8 composed as follows of lithium ion power battery cathode pole piece material:
Barrier film is: the single-layer septum of PP material
Electrolyte is: 1.2mol/L LiPF
6solution, solvent composition is EC:DMC:EMC=1:1:1
Shell is plastic casing
Concrete preparation method is as follows:
1) making of positive plate: add positive electrode by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain anode sizing agent, anode sizing agent is uniformly coated on 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: add negative material by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain cathode size, cathode size is uniformly coated on 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, after 16 hours, are laminated into battery core together by positive plate, barrier film, negative plate, insert in plastic casing, become semi-finished product battery;
4) by the 80 ℃ of bakings after 72 hours under-0.09MPa of semi-finished product battery, fluid injection, change into, partial volume becomes 120Ah battery.
Claims (1)
1. a lithium-ion-power cell, it is characterized in that: negative material is comprised of the raw material of following mass percent: 94% lithium titanate, 3% adhesive LA132,3% electrically conductive graphite, positive electrode is comprised of the raw material of following mass percent: 91% LiFePO 4,1% adhesive LA132,8% superconduction carbon black; Barrier film is: the single-layer septum of PP material, electrolyte is: 1.2mol/L LiPF
6solution, solvent composition is EC:DMC:EMC=1:1:1, concrete preparation method is as follows:
1) making of positive plate: add positive electrode by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain anode sizing agent, anode sizing agent is uniformly coated on 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: add negative material by formula ratio, be dissolved in water, even by double star power mixer high-speed stirred, eliminate bubble, iron filings, obtain cathode size, cathode size is uniformly coated on 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, after 12 hours, are laminated into battery core together by positive plate, barrier film, negative plate, insert in plastic casing, become semi-finished product battery;
4) by the 90 ℃ of bakings after 48 hours under-0.10MPa of semi-finished product battery, fluid injection, change into, partial volume becomes 120Ah battery.
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