CN101436654A - Ferric phosphate lithium type safety high power lithium ion battery - Google Patents
Ferric phosphate lithium type safety high power lithium ion battery Download PDFInfo
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- CN101436654A CN101436654A CNA2007101244639A CN200710124463A CN101436654A CN 101436654 A CN101436654 A CN 101436654A CN A2007101244639 A CNA2007101244639 A CN A2007101244639A CN 200710124463 A CN200710124463 A CN 200710124463A CN 101436654 A CN101436654 A CN 101436654A
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Abstract
The invention discloses a lithium iron phosphate type safe high-power lithium ion battery, which comprises a positive pole, a negative pole, a diaphragm and a nonaqueous electrolytic solution. The positive pole is prepared by coating a mixture consisting of an active material, a conductive agent and a binder on two sides of a metal aluminum foil, while the negative pole is prepared by coating the mixture consisting of the active material, the conductive agent and the binder on two sides of a metal copper foil, wherein the components of the coating mixture of the positive pole in percentage by mass respectively are: 80 to 95 percent of the active material lithium iron phosphate, 1 to 15 percent of the conductive agent, and 2 to 10 percent of the binder; and the components of the coating mixture of the negative pole in percentage by mass percentage respectively are: 90 to 97 percent of the active material, 0 to 3 percent of the conductive agent, and 2 to 7 percent of the binder. With the invention, the lithium ion battery is safer and has high multiplying power discharging performance, and the security hidden trouble problems caused when the lithium ion battery is applied to a high multiplying power discharging field are greatly reduced.
Description
Technical field
The invention belongs to the technical field of lithium ion battery, particularly relate to a kind of ferric phosphate lithium type safety high power lithium ion battery.
Background technology
Lithium ion battery with its have operating voltage height, energy density big, have extended cycle life, self discharge is little, the advantage of memory-less effect, be widely used in fields such as mobile phone, notebook computer, PDA, digital camera, MP3, become various modern communication equipment and the indispensable parts of electronic equipment.
Along with the renewal and the development of technology, the development of various power consumption equipments requires battery to have thinner, lighter, higher energy density and power density and higher fail safe to the demands for higher performance of battery.The particularly nervous and various electric motor cars of the energy, the development of hybrid vehicle in recent years, its manufacturer seek always a kind of in light weight, volume is little, environmentally friendly, can heavy-current discharge and product with higher safety performance.
Though present lithium ion battery can provide higher discharging current,, there is great potential safety hazard when causing consuming device to use because the fail safe of electrode used therein material is lower.Because the fast development that electric tool is used in different field, it not only requires battery will have the performance of heavy-current discharge, and to have higher safety performance, adopt the high security material ferric lithium phosphate is that positive electrode has been done further improvement to the security performance of high power lithium ion cell for this reason.
Summary of the invention
In order to overcome an above-mentioned difficult problem, the objective of the invention is to propose a kind of safe and ferric phosphate lithium type lithium ion battery that have big multiplying power discharging property, significantly reduce lithium ion battery and be applied to the safety issue that the high-multiplying power discharge field is brought.
The present invention is achieved through the following technical solutions:
A kind of ferric phosphate lithium type safety high power lithium ion battery, comprise positive pole, negative pole, barrier film and nonaqueous electrolytic solution, positive pole is the mixture that active material, conductive agent and binding agent are formed is uniformly coated on the metal aluminum foil two sides and makes, negative pole is with active material, the mixture that conductive agent and binding agent are formed is uniformly coated on the metal copper foil two sides and makes, and wherein: the mass percent of active material LiFePO4, conductive agent, binding agent is respectively 80～95%, 1～15%, 2～10% in the described anodal coating mixture; The mass percent of active material, conductive agent, binding agent is respectively 90～97%, 0～3%, 2～7% in the described negative pole coating mixture.
The present invention can also further take following technical measures to realize:
Described positive electrode active materials is distributed in LiFePO4 (LiFePO between 0.1～20 μ m for grain diameter D50
4), conductive agent is one or more materials of conductive carbon black with high conductivity, electrically conductive graphite, carbon fiber, carbon nano-tube, as a kind of material or the two or more composition in acetylene black, super conductive carbon black (Super-P), electrically conductive graphite (KS-6), the gas-phase growth of carbon fibre (VGCF); Binding agent is the homopolymers (PVDF) of the Kynoar of molecular weight between 20～1,200,000.
Described negative active core-shell material is one or more a composition of the Delanium of particle size distribution between 1～30 μ m; Conductive agent is one or more materials in conductive carbon black with high conductivity, electrically conductive graphite, carbon fiber, the carbon nano-tube, as a kind of material or the two or more composition in super conductive carbon black (Super-P), electrically conductive graphite (SFG-6, SFG-15), the gas-phase growth of carbon fibre (VGCF); Binding agent is the composition or the oiliness binding agent PVDF of aqueous binders butadiene-styrene rubber breast (SBR) and sodium carboxymethylcellulose (CMC).
Described positive pole ear is that ultrasonic bond is welded on the aluminium strip on the plus plate current-collecting body, and width is between 2～20mm; Described negative lug is that ultrasonic bond is welded on nickel strap, copper nickel composite band or the copper strips on the negative current collector, and width is between 2～20mm.
Described barrier film is three layers of composite diaphragm of polypropylene-polyethylene-polypropylene (PP-PE-PP) or monolayer polyethylene PE barrier film, and thickness is between 12～25 μ m.
Described plus plate current-collecting body is the aluminium foil of thickness between 12～30 μ m; Negative current collector is the Copper Foil of thickness between 8～20 μ m.
Described positive plate lug number is 1～6, and described negative electrode lug number is 1～6.
Described both positive and negative polarity group is stacked or takeup type, and the electrode compacted depth is between 60～170 μ m.
Described electrolyte is by lithium hexafluoro phosphate (LiPF
6) or LiBF4 (LiBF
4) mix composition with two or more material in ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) organic solvent.
The present invention has the following advantages and good effect:
1, its discharging current can reach 1～20C discharge, and 15C discharge battery surface temperature is lower than 60 ℃.
2,300 capability retentions of lithium ion battery 10C discharge cycles that adopt this scheme to make can reach more than 80%.
3, adopt the 15C of the lithium ion battery that this scheme makes and the ratio of 1C discharge capacity can reach more than 95% respectively.
4, manufacture craft is simple, and battery has higher safety performance, and battery all overcharges by 3C/10V, 130 ℃/30min thermal shock, short circuit, destructive tests such as acupuncture.
Description of drawings
Fig. 1 is the profile schematic diagram of safety high power lithium ion battery of the present invention;
Fig. 2 is the takeup type pole piece shape of safety high power lithium ion battery of the present invention;
Fig. 3 is the stacked pole piece shape of safety high power lithium ion battery of the present invention;
Fig. 4 is the 1C discharge curve of safety high power lithium ion battery of the present invention;
Fig. 5 is the 5C discharge curve of safety high power lithium ion battery of the present invention;
Fig. 6 is the 10C discharge curve of safety high power lithium ion battery of the present invention;
Fig. 7 is the 15C discharge curve of safety high power lithium ion battery of the present invention.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, enumerate following examples now, and conjunction with figs. is described in detail as follows:
Manufacturing process with 100～1600mAh safety high power lithium ion battery is that example is illustrated, battery structure as shown in Figure 1, the making of battery is implemented as follows:
Anodal preparation: with N-dimethyl pyrrolidone (NMP) is solvent, the LiFePO4 that grain diameter D50 is distributed between 0.1～20 μ m is a positive active material, super conductive carbon black (Super-P) is a conductive agent, the polyvinylidene fluoride homopolymer (PVDF) of molecular weight between 20～1,200,000 is binding agent, the use amount of NMP is added according to particle size, the particle size distribution difference of LiFePO4, and its slurry viscosity control range is 3000～20000cP.The used mass percent of present embodiment is: LiFePO
4: Super-P:PVDF:NMP=88:4:8:110.At first fully be dissolved in PVDF among the NMP, then it is joined in the super conductive carbon black and LiFePO4 mixed powder that has been pre-mixed, evenly stir the de-bubble of 4～5h final vacuum fast, at last prepared slurry is evenly coated thickness on the collector aluminium foil between 12～30 μ m, drying, roll-in, carry out lug spot welding after cutting, lug is the aluminium strip of width between 2～20mm, and the lug number is 1～6, finishes the making (as shown in Figure 2) of positive plate.
The preparation of negative pole: with H
2O is a solvent, the Delanium (carbonaceous mesophase spherules MCMB) of particle size distribution between 1～30 μ m is negative electrode active material, super conductive carbon black (Super-P) is a conductive agent, aqueous binders butadiene-styrene rubber breast (SBR) is a binding agent with the mixture of sodium carboxymethylcellulose (CMC), the consumption of water adds according to particle size, the particle size distribution difference of the graphite that uses, its adding proportion is between 110～170, and the used mass percent of present embodiment is: MCMB:Super-P:CMC:SBR:H
2O=90:5:2:3:130.At first CMC is scattered in H uniformly
2Among the O, join several times then in the super conductive carbon black and graphite mixed powder that is pre-mixed, the back adding SBR that stirs stirs once more, vacuumize de-bubble evenly, at last prepared slurry is evenly coated thickness on the copper foil of affluxion body between 8～20 μ m, drying, roll-in, carried out lug spot welding after cutting, lug is nickel strap, copper nickel composite band or the copper strips of width between 2～20mm, the lug number is 1～6, finishes the making (as shown in Figure 2) of negative plate.
Electrolyte uses the LiPF that is dissolved with 1mol/L
6With volume ratio be the solution of the EC+DEC+DMC mixed solvent of 1:1:1.
It is the microporous polyethylene film of 20 μ m that barrier film adopts thickness.
The positive and negative electrode pole piece that branch is cut and handle after membrane coil coiled utmost point group, the electrode compacted depth is between 80～170 μ m, injects above-mentioned electrolyte and seals, and finishes battery and makes (as shown in Figure 1).
Present embodiment uses barrier film identical with embodiment 1 with electrolyte.
Anodal preparation: with N-dimethyl pyrrolidone (NMP) is solvent, the LiFePO4 that grain diameter D50 is distributed between 0.1～20 μ m is a positive active material, the mixture of super conductive carbon black (Super-P) and electrically conductive graphite (KS-6) is a conductive agent, the polyvinylidene fluoride homopolymer (PVDF) of molecular weight between 20～1,200,000 is binding agent, the use amount of NMP is added according to the particle size of LiFePO4, the difference of particle size distribution, and its slurry viscosity control range is 3000～20000cP.The used mass percent of present embodiment is: LiFePO
4: Super-P:KS-6:PVDF:NMP=90:3:1:6:130.At first fully be dissolved in PVDF among the NMP, then it is joined in the conductive agent (Super-P+KS-6) and LiFePO4 mixed powder that has been pre-mixed, evenly stir the de-bubble of 4～5h final vacuum fast, at last prepared slurry is evenly coated thickness on the collector aluminium foil between 12～30 μ m, drying, roll-in, carry out lug spot welding after cutting, lug is the aluminium strip of width between 2～20mm, and the lug number is 1～4, finishes the making (as shown in Figure 2) of positive plate.
The preparation of negative pole: with H
2O is a solvent, the Delanium (carbonaceous mesophase spherules MCMB) of particle size distribution between 1～30 μ m is negative electrode active material, super conductive carbon black (Super-P) and electrically conductive graphite (SFG-15) are conductive agent, aqueous binders butadiene-styrene rubber breast (SBR) is binding agent with the mixture of sodium carboxymethylcellulose (CMC), the consumption of water adds according to particle size, the particle size distribution difference of the graphite that uses, its adding proportion is between 110～170, and the used mass percent of present embodiment is: MCMB:Super-P:SFG-15:CMC:SBR:H
2O=92:2:1:2:3:130.At first CMC is scattered in H uniformly
2Among the O, join several times then in the super conductive carbon black conductive agent and graphite mixed powder that is pre-mixed, the back adding SBR that stirs stirs once more, vacuumize de-bubble evenly, at last prepared slurry is evenly coated thickness on the copper foil of affluxion body between 8～20 μ m, drying, roll-in, carried out lug spot welding after cutting, lug is nickel strap, copper nickel composite band or the copper strips of width between 2～20mm, the lug number is 1～6, finishes the making (as shown in Figure 2) of negative plate.
The positive and negative electrode pole piece that branch is cut and handle after membrane coil coiled utmost point group, the electrode compacted depth is between 60～170 μ m, injects above-mentioned electrolyte and seals, and finishes battery and makes (as shown in Figure 1).
As Fig. 4～7 is the different current discharge curves that embodiment 2 makes battery.The battery charging and discharging voltage range is 2.0～3.8V, and the ratio of 15C discharge capacity and 1C is 97.9%.
The manufacture method of its positive and negative plate and the barrier film of use and electrolyte all with embodiment 1 in consistent, but the shape of positive and negative plate and assembling mode and embodiment 1 are inconsistent, embodiment 1 adopts winding method to carry out, embodiment 4 adopts the lamination modes to carry out.To be die-cut into shape shown in Figure 3 with sheet-punching machine according to the positive and negative plate that the mode of embodiment 1 is made, make up the poling group by positive pole, barrier film, negative pole, barrier film, anodal sequential cascade again, the electrode compacted depth is between 60～170 μ m, injection electrolyte also seals, and finishes battery and makes.
Claims (10)
1, a kind of ferric phosphate lithium type safety high power lithium ion battery, comprise positive pole, negative pole, barrier film and nonaqueous electrolytic solution, positive pole is the mixture that active material, conductive agent and binding agent are formed is coated on the metal aluminum foil two sides and makes, negative pole is the mixture that active material, conductive agent and binding agent are formed is coated on the metal copper foil two sides and makes, and it is characterized in that: the mass percent of active material LiFePO4, conductive agent, binding agent is respectively 80～95%, 1～15%, 2～10% in the described anodal coating mixture; The mass percent of active material, conductive agent, binding agent is respectively 90～97%, 0～3%, 2～7% in the described negative pole coating mixture.
2, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described positive electrode active materials is distributed in LiFePO4 LiFePO between 0.1～20 μ m for grain diameter D50
4Conductive agent is conductive carbon black Super-P, electrically conductive graphite SFG-6, the carbon fiber of high conductivity, one or more materials of carbon nano-tube, binding agent is the homopolymers PVDF of the Kynoar of molecular weight between 20～1,200,000, with N-dimethyl pyrrolidone NMP is solvent, and mass percent is: LiFePO
4: Super-P:PVDF:NMP=88:4:8:110.
3, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described negative active core-shell material is one or more a composition of the Delanium of particle size distribution between 1～30 μ m; Conductive agent is conductive carbon black Super-P, electrically conductive graphite SFG-6, the carbon fiber of high conductivity, one or more materials in the carbon nano-tube, and binding agent is composition or the oiliness binding agent PVDF of aqueous binders butadiene-styrene rubber breast SBR and sodium carboxymethylcellulose CMC.
4, ferric phosphate lithium type safety high power lithium ion battery according to claim 3, it is characterized in that: described negative electrode active material is selected carbonaceous mesophase spherules MCMB for use, conductive agent is selected super conductive carbon black Super-P for use, binding agent is selected aqueous binders butadiene-styrene rubber breast SBR and sodium carboxymethylcellulose CMC, each material and aqueous solvent H for use
2The mass percent of O is: MCMB:Super-P:CMC:SBR:H
2O=90:5:2:3:130.
5, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described positive pole ear is that ultrasonic bond is welded on the aluminium strip on the plus plate current-collecting body, and width is between 2～20mm; Described negative lug is that ultrasonic bond is welded on nickel strap, copper nickel composite band or the copper strips on the negative current collector, and width is between 2～20mm.
6, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described barrier film is polypropylene PP-polythene PE-three layers of composite diaphragm of polypropylene PP or monolayer polyethylene PE barrier film, and thickness is between 12～25 μ m.
7, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described plus plate current-collecting body is the aluminium foil of thickness between 12～30 μ m; Negative current collector is the Copper Foil of thickness between 8～20 μ m.
8, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described positive plate lug number is 1～6, and described negative electrode lug number is 1～6.
9, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described both positive and negative polarity group is stacked or takeup type, and the electrode compacted depth is between 60～170 μ m.
10, ferric phosphate lithium type safety high power lithium ion battery according to claim 1 is characterized in that: described electrolyte is by lithium hexafluoro phosphate LiPF
6Or LiBF4 LiBF
4Mix composition with two or more material in ethylene carbonate EC, propene carbonate PC, dimethyl carbonate DMC, methyl ethyl carbonate EMC and the diethyl carbonate DEC organic solvent.
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