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:
With reference to accompanying drawing 1-3, arrow is the coiling direction of electrode.Positive electrode active materials coat 1 of the present invention adopts the cobalt-lithium oxide active material; A kind of active material that negative active core-shell material coat 6 comprises carbon fiber and selects from spherical graphite or flaky graphite at least, wherein the content of carbon fiber is greater than 1wt%, less than 5wt%; The double spread weight of described positive electrode active materials coat 1 and negative active core-shell material coat 6 is respectively 10mg-30mg/cm
2, 4.8mg-14.5mg/cm
2
For takeup type electricity core, because the influence of inner ring curvature, positive pole ear 3 and negative lug 8 can not be too wide, according to battery capacity and lug the difference of density are set, and the width of positive pole ear 3 and negative lug 8 is 5mm-20mm, and optimum width is 6-12mm; Simultaneously for preventing to use wide outside weld lug when bending is reeled, to cause damage even short circuit to electrode, positive pole ear 3 and negative lug 8 are left curtain shape positive pole ear sheared edge 5 and negative lug sheared edge 10 with plus plate current-collecting body 2 and negative current collector 7 laps respectively, and weld with corresponding collector one by one.Positive pole ear 3 and negative lug 8 ends are respectively equipped with positive pole ear riveted holes 4 and negative lug riveted holes 9.When positive pole ear 3 and plus plate current-collecting body 2, negative lug 8 and negative current collector 7 were integral structure, its transitional region was the class arc or the triangular structure of being wider than lug.
Positive pole ear 3 is an aluminium strip, is welded on the plus plate current-collecting body 2 its sectional area S by ultrasonic bond
1With adjacent positive lug 3 interval d
1And positive electrode active materials coat 1 width w
1Satisfy following formula: 1 * 10
-5≤ S
1/ (d
1* w
1)≤4 * 10
-5, and the thickness of positive pole ear 3 is not more than 1.5 times of anodal thickness.Because if S
1/ (d
1* w
1)<1 * 10
-5Then cause internal resistance bigger, it is too high to understand temperature rise during heavy-current discharge, influences fail safe and cycle life.S
1/ (d
1* w
1)>4 * 10
-5The time, the then excessive preparation that influences battery of lug.If the thickness of positive pole ear 3 is greater than 1.5 of anodal thickness, welding and other operations then are difficult to carry out.Certainly, the blank of electrode is reserved enough width, also can determine lug from reserving blank space, and its width satisfies the following formula requirement with same requirement the at interval, and but, because aluminium foil is thinner, therefore the preferred ratio lower limit promptly adopts the lug of broad in above-mentioned scope.
Negative lug 8 is nickel matter or copper strip, is welded on the negative current collector 7 the sectional area S of nickel strap or copper strips by ultrasonic bond
2With adjacent cathode lug 4 interval d
2And negative active core-shell material coat 6 width w
2Satisfy following formula: 1 * 10
-5≤ S
2/ (d
2* w
2)≤3 * 10
-5, and the thickness of lug is not more than 1.5 times of negative pole thickness.Similar with positive pole, because if S
2/ (d
2* w
2)<1 * 10
-5Then cause internal resistance bigger, it is too high to understand temperature rise during heavy-current discharge, influences fail safe and cycle life.S
2/ (d
2* w
2)>4 * 10
-5The time, the then negative lug 8 excessive preparations that influence battery.The thickness of negative lug 8 is not more than 1.5 times of negative pole thickness for well in addition, if greater than 1.5 times then blocked up, welding and other operations are difficult to carry out.Certainly, the blank of electrode is reserved enough width, also can determine negative lug 8 from reserving blank space, and its width satisfies the following formula requirement with same requirement the at interval, and but, because Copper Foil is thinner, therefore the preferred ratio lower limit promptly adopts the lug of broad in above-mentioned scope.
Because aluminium very easily forms oxide-film, influence its electric conductivity, so the number of positive pole ear 3 or the gross area are greater than the number or the gross area of negative lug 8.
Though adopted cobalt-lithium oxide as positive electrode active materials herein simultaneously, the present invention is not limited in cobalt-lithium oxide, the composition formula that can be used for positive electrode active materials of the present invention is Li
xMO
2, Li
yM
2O
4The composite oxides of (M is more than one transition metal in the formula, 0≤x≤1,0≤y≤2), and chalcogen compound or oxide with tunnel or layer structure.Its instantiation can be enumerated as LiNiO
2, LiCo
xNi
1-xO
2, LiNi
xCo
yNi
1-x-yO
2, LiMn
2O
4, Li
2Mn
2O
4, LiNi
0.5Mn
1.5O
4,, LiFePO
4, MnO
2, FeO
2, V
2O
5, V
6O
13, TiO
2, TiS
2Deng.Certainly the derivative that also comprises the above-claimed cpd that elements such as aluminium, Mg mix.In addition, organic compound also can be used as positive electrode active materials of the present invention such as conducting polymers such as polypyrrole, polyanilines.And no matter be inorganic compound or organic compound, above-mentioned all cpds also can mix use.
As lithium ion battery of the present invention, positive pole preferably comprises the carbon nano-fiber of failing to grow up in 20 microns, and its addition is no more than 10wt% with respect to anodal coating gross weight.This is because a certain amount of by adding, the carbon nano-fiber of certain-length, can fully guarantee in the electrode between active material and and collector between conductivity.Simultaneously, can make that again the combination property of electrode is guaranteed.The length of fiber surpasses 20 microns, then might make the part fiber pass barrier film and arrive electrode, causes the micro-short circuit between positive/negative plate.In addition, if addition surpasses 10wt%, then must add the adhesive force that a large amount of binding agents could keep electrode material layer simultaneously.Excessive binding agent then is the reason that causes the electrode internal resistance to raise.Therefore, the addition of carbon nano-fiber is to be no more than 10wt% for well.
The present invention has used gas-phase grown nanometer carbon fibre (VGCF), acetylene black (AB), also can use carbon black and stable metal nano fiber such as Ni etc. in addition.Optimum fiber shape electric conducting material.Because fibrous electric conducting material is suitable for the conduction approach of keeping.
Though enumerated spherical graphite and scale shape graphite, can be used for that negative active core-shell material of the present invention is not limited only to this, other can be listed below as can be used for negative material of the present invention, can form the metallic element such as the aluminium of alloy with Li, Si, Pb, Sn, Zn etc., transition metal oxide such as NiO, CoO, Co
2O
3, CuO etc., also have LiFe
2O
3, Nb
2O
3, WO
2, MoO
2,, the metal oxide of SiO etc., the easily carbonaceous material of graphitized carbon material and hard carbon etc. and the mixture of above-mentioned material.That considers battery discharges and recharges life-span and fail safe, preferred carbonaceous material.
As electrolyte of the present invention, can comprise one or more mixture of following organic solvent.Ethyl carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC), diethyl carbonate (DEC), gamma-butyrolacton (GBL), sulfolane, methyl-sulfoxide, second moon green grass or young crops (AN), dimethyl formamide, diethylformamide, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, oxolane (THF), 2-methyltetrahydrofuran, dioxolanes, methyl acetic acid ester isopolarity solvent.For obtaining good cell discharge performance and life-span, preferably make and in above-mentioned solvent, contain ethylene carbonate (EC).
The electrolytic salt that is dissolved in the electrolyte solvent can comprise following single electrolytic salt and composition thereof.LiPF for example
6, LiClO
4, LiBF
4, LiAsF
6, LiCF
3CO
2, LiCF
3(CF)
3, LiCF
3(C
2F
5)
3, LiCF
3SO
3, LiN (SO
2CF
3)
2, LiN (SO
2CF
2CF
3)
2, LiN (COCF
3)
2, LiN (COCF
2CF
3)
2And LiPF
3(CF
2CF
3)
3Be preferably in and partly contain LiPF in the electrolytic salt
6Or LiBF
4, and can on negative pole, form good epithelium and obtain good flash-over characteristic and life-span.
Grow up, preferably add additive vinylene carbonate (VC) and derivative thereof for the transition that suppresses irreversible capacity and negative material surface SEI epithelium simultaneously, as 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, 4,5-dipropyl vinylene carbonate, 4-ethyl-5-methyl carbonic acid vinylene, 4-ethyl-5-propyl group vinylene carbonate.Annular in addition sulfuric ester also helps forming good SEI, as glycol sulfate, 1,2-propylene glycol sulfuric ester, 1,2-butanediol sulfuric ester, 1,3-butanediol sulfuric ester, 2,3-butanediol, benzoglycols sulfuric ester etc.
Barrier film of the present invention can adopt braid, non-woven fabric, micropore synthetic resin film etc.In the above-mentioned diaphragm material, the polyolefin micro-porous film of special preferred microporous synthetic resin film, especially preferably polyethylene and microporous polypropylene membrane or their composite micro porous film etc.The adopted reason of these TPO micro-porous films is that it is better than thickness preferably, film-strength, film resistance characteristic.
If the employing colloidal electrolyte, then it can doublely do separator again.In this case, can use porose copolymer solid electrolyte, make it contain electrolyte again.
Battery of the present invention can be made into column type, oval, square, button shaped and the folded film flexible package of aluminium etc.Capacity can be tens of mAh to tens of Ah even more than the 100Ah.But when making high capacity lithium ion battery, with column type, oval, square for well.
Embodiment 1
Anodal preparation:
Take by weighing the LiCoO of the 93wt% of positive electrode active materials
2N-N-methyl-2-2-pyrrolidone N-(NMP) solution of polyvinylidene fluoride (PVdF) bonding agent and to make the content of PVdF be 4.5wt%, 2.5wt% (VGCF) as electric conducting material, the three is mixed the formation cathode mix, in mixture, add NMP and prepare pastel with mixer, then this pastel is coated onto equably continuously the two sides that thickness is 20 μ m aluminium foils, the width of filming is 220mm, leave the blank of 20mm at side tow sides of aluminium foil, drying again, after the roll-in, branch cuts away an opposite side (not blanking) of 20mm blank and makes the wide 200mm of coating, the positive plate of the wide blank of 20mm.Coating weight is 22mg/cm
2
The preparation of negative pole:
In weight 60% carbonaceous mesophase spherules MCMB, 30% flaky graphite, weight is that 2% VGCF and weight are that 8% PVdF (the solution mode with NMP adds) makes pastel, it is identical with positive pole then this pastel to be coated onto equably continuously two sides, coating method that thickness is 10 μ m Copper Foils, drying again, roll-in and make negative plate.Coating weight is 10mg/cm
2
The welding of positive pole ear:
As shown in Figure 1: at first selecting for use thick is 100 microns, wide be the aluminium strip of 10mm as positive pole ear 3, opening the 30mm mouth, make aluminium strip one side be divided into two parts with plus plate current-collecting body 2 welding one side, opposite side is provided with positive pole ear riveted holes 4, is used for riveted and fixed in Positive Poles.With ultrasonic bonder two parts aluminium strip four means of spot welds of dividing equally are fixed on the plus plate current-collecting body 2 then,, weld next positive pole ear 3 again at interval 200mm place, by that analogy with same method.The lug parameter S that obtains thus
1/ (d
1* w
1) be 2.5 * 10
-5
The welding of negative lug:
As shown in Figure 2: selecting for use thick is 100 microns, wide be the nickel strap of 10mm as negative lug 8, opening the 30mm mouth, make negative lug 8 one sides be divided into 2 parts with negative current collector 7 welding one side, opposite side is provided with negative lug riveted holes 9, is used for riveted and fixed at the negative pole pole.With ultrasonic bonder two parts nickel strap four means of spot welds of dividing equally are fixed on the negative current collector 7 then,, weld next negative lug 8 again at interval 200mm place, by that analogy with same method.The lug parameter S that obtains thus
2/ (d
2* w
2) be 2.5 * 10
-5
The microporous polyethylene film that is about 25 microns with thickness is made diaphragm body.
The nonaqueous electrolyte that uses is for being dissolved with 1mol/l LiPF
6, 1: 1: 1 EC+DEC+DMC mixed solvent solution of volume ratio adds the vinylene carbonate of relative electrolyte total amount 1.0wt% on this basis.The assembling of 35Ah battery:
The active material coating is faced with the alternate positive of barrier film, positive and negative, lug is in an opposite side.Stack that positive pole, barrier film, negative pole are entwined electric core, insert cylinder, the good lug of riveting, weld electrode cap, fluid injection is sealed again after 60 ℃ of vacuumize.So be assembled into the 35Ah battery as battery A1, and carry out electro-chemical test and temperature survey as follows.
Discharge and recharge and the case temperature test:
At first carry out volume test: be charged as the CC-CV pattern; Discharge is the CC pattern.Promptly use 0.2C multiplying power constant current charge to 4.2V, the 4.2V constant voltage is 2 hours then; Discharge ends to 2.75V with 0.2C multiplying power constant current discharge equally.The discharge capacity that obtains in order to last method is as initial capacity.Carry out the multiplying power discharging experiment then, promptly same with volume test, all be charged to 4.2V with CC-CV, respectively to be equivalent to 5C, the 10C constant current discharge is to 2.5V, with the capacity of this capacity that obtains as each multiplying power discharging again.And, when big multiplying power discharging, detect the variations in temperature of housing outer wall central part with thermistor.All treat again residual capacity to be carried out recharging after low range (0.2C) discharges into 2.75V after voltage (OCV) recovers at every turn.Discharging and recharging by above method and temperature detection result is organized in the table 1.Fig. 3 is each multiplying power discharging and the battery surface temperature variation of battery.
Embodiment 2
Except d1, d2 changes into beyond the 300mm, other all identical and made battery A2 of the present invention with embodiment 1, its measurement result is recited in the table 1 equally.
Embodiment 3
Except d2 changes 500mm into, other all identical and made battery A3 of the present invention with embodiment 1, its measurement result is recited in the table 1 equally.
Embodiment 4
Except d1 changes 500mm into, other all identical and made battery A4 of the present invention with embodiment 1, its measurement result is recited in the table 1 equally.
Embodiment 5
Except the positive and negative electrode lug changes 50 micron thickness (S1, S2=0.5mm into
2), other all identical and made battery A5 of the present invention with embodiment 1, its measurement result is recited in the table 1 equally.
Comparative Examples 1
Except d2 changes 600mm into, other all identical and made battery B1 of the present invention with embodiment 1, its measurement result is recited in the table 1 equally.
Comparative Examples 2
Except d1, d2 changes into beyond the 600mm, other all identical and made battery B2 of the present invention with embodiment 1, its measurement result is recited in the table 1 equally.
Table 1
Battery |
d1(mm) |
w1(mm) |
S1(mm
2)
|
S1/(d1×w1) (×10
-5)
|
d2(mm) |
w2(mm) |
S2(mm
2)
|
S2/(d2×w 2)(×10
-5)
|
Capacity (Ah) |
Voltage platform (V) |
Temperature (℃) |
Embodiment A 1 |
200 |
200 |
1 |
2.5 |
200 |
200 |
1 |
2.5 |
34.2 |
3.34 |
68 |
Embodiment A 2 |
300 |
200 |
1 |
1.67 |
300 |
200 |
1 |
1.67 |
33.5 |
3.32 |
71 |
Embodiment A 3 |
200 |
200 |
1 |
2.5 |
500 |
200 |
1 |
1.0 |
32 |
3.25 |
73 |
Embodiment A 4 |
500 |
200 |
1 |
1.0 |
200 |
200 |
1 |
2.5 |
30 |
3.20 |
74.3 |
Embodiment A 5 |
200 |
200 |
0.5 |
1.25 |
200 |
200 |
0.5 |
1.25 |
28 |
3.10 |
76 |
Comparative Examples B1 |
200 |
200 |
1 |
2.5 |
600 |
200 |
1 |
0.83 |
25 |
2.95 |
81 |
Comparative Examples B2 (7C) |
600 |
200 |
1 |
0.83 |
600 |
200 |
1 |
0.83 |
16 |
2.71 |
82 |
Can know clearly from the result of table 1: adopt film continuously, embodiment battery A1-A4 discharge capacity that the side goes out extreme ear structure is big, voltage platform is very high (>3.2V), high temperature rise is little.But when the lug spacing is excessive, internal resistance increases, big multiplying power discharging capacity is little, voltage platform is low, temperature rise, surface temperature even be higher than 80 ℃, though in table, do not show simultaneously, but know that very it is after 50 circulations that the A1 capacity is reduced to 80% of initial capacity, and only circulated 3 times, B2 of B1 are that 10 times (7C), B3 are 15 times (7C).So the coating that contains active material of anodal and negative electrode is continuous coated, and leaves the collector blank in the side along coiling direction of electrode, leave electric current in blank space and derive lug, and the lug of positive pole is aluminium strip, the sectional area S of aluminium strip lug
1With lug interval d
1And anodal coating width w
1Satisfy following formula: 1 * 10
-5≤ S
1/ (d
1* w
1)≤4 * 10
-5, and the thickness of lug is not more than 1.5 times of anodal thickness; The lug of negative pole is nickel matter or copper strip, is welded on the negative current collector sectional area S of nickel or copper strips lug by ultrasonic bond
2With lug interval d
2And negative pole coating width w
2Satisfy following formula: 1 * 10
-5≤ S
2/ (d
2* w
2)≤3 * 10
-5, and the thickness of lug is not more than 1.5 times of negative pole thickness, to the high-multiplying power discharge capacity of battery, to suppress temperature rise and improve cycle life be effective.