CN102738500B - Lithium battery and manufacturing method thereof - Google Patents
Lithium battery and manufacturing method thereof Download PDFInfo
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- CN102738500B CN102738500B CN201110090275.5A CN201110090275A CN102738500B CN 102738500 B CN102738500 B CN 102738500B CN 201110090275 A CN201110090275 A CN 201110090275A CN 102738500 B CN102738500 B CN 102738500B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a lithium battery and a manufacturing method thereof. The lithium battery comprises an anode, a cathode, a diaphragm and an electrolyte solution, wherein the cathode is opposite to the anode; the diaphragm is positioned between the anode and the cathode, and the anode, the cathode and the diaphragm limit an accommodation area together; and the electrolyte solution comprises an organic solvent, a lithium salt and an additive, the additive comprises a maleimide base compound and a hydroxy group-containing substance, the molecular weight of the hydroxy group-containing substance is less than 1000, and the content of the hydroxy group-containing substance in the electrolyte solution is 0.05-5wt%. According to the lithium battery and the manufacturing method of the invention, a problem that water exists in the battery can be solved, and process steps can be carried out without a high-dryness fraction and low water content environment, so it is helpful for reducing the making cost and improving performances of the battery.
Description
Technical field
The present invention relates to lithium battery, particularly the electrolyte solution of lithium battery.
Background technology
Because primary cell does not meet environmental requirement, therefore chargeable secondary battery system comes into one's own gradually in recent years.Now portable type electronic product all needs light-weighted battery as digital camera, mobile phone, notebook computer, and along with the fast development of portable type electronic product and universal, this can recharge the feature such as the lithium battery of electric discharge, high-voltage value lightweight owing to having concurrently and high-energy-density, and its market demand is grown with each passing day.Compared with traditional lead accumulator, Ni-MH battery, nickel-zinc cell, nickel-cadmium cell, lithium battery has that operating voltage is high, energy density is large, lightweight, the life-span is long and the advantage such as the feature of environmental protection is good, is also the optimal selection that will be applied to bendable battery future.Therefore, now also more and more higher to the requirement of the performance of lithium battery such as light durable, high voltage, high-energy-density and high security etc., lithium battery especially application and the development potentiality in LEV (Light Electric Vehicle), electric motor car, large-scale accumulate industry is high.
But, in current known technology, the manufacturing process of lithium battery must be carried out under the environment of high aridity low water content, and its main cause is that water can electrolysis become oxygen and hydrogen in cell electrochemical reaction, thereby easily causes cell expansion and performance degradation.In addition, in battery, the water of high-load also can carry out side reaction and form hydrofluoric acid with lithium salts, and this product will cause the problem such as transition metal ions stripping and the corrosion of collector of electrode material, thereby is very easy to make battery to cause danger.Because lithium battery must be in the lower manufacture of the environment of high aridity low water content (as relative humidity < 5%), overwhelming majority manufacturers all need to build hothouse and technological requirement is produced and assembled to tackle to dry factory building, therefore cause lithium battery manufacturer at electric power the sky high cost aspect paying.On the other hand, utilizing air chamber (air chamber) mode to carry out secondary encapsulation procedure improves high water content in battery and also has problems.Above-mentioned secondary encapsulation is to instigate the electrolysis in electrochemical reaction for the first time of high-load water in battery to generate gas, and the first headspace of battery makes gas can flow to air chamber, and then air chamber is removed and carry out secondary encapsulation, the therefore various complexity of processing step and expend time in longer.But, no matter be the manufacturing process of carrying out above-mentioned which kind of mode, all extra manufacturing costs that increases of extremely not convenient and meeting.
Summary of the invention
Therefore, the invention provides the lithium battery of the battery performance with improvement.
The present invention also provides lithium battery manufacture method, and it can carry out under the atmospheric environment of low aridity or general aridity.
The present invention proposes lithium battery, and it comprises anode, negative electrode, barrier film and electrolyte solution.Negative electrode and positive electrode is relative.Barrier film is between anode and negative electrode, and its Anodic, negative electrode and barrier film limit holding area jointly.Electrolyte solution is arranged in holding area, and wherein electrolyte solution comprises organic solvent, lithium salts and additive.Additive comprises compound and the hydroxyl material based on maleimide, and wherein the molecular weight of hydroxyl material is less than 1000, and the content of hydroxyl material in electrolyte solution is 0.05 % by weight to 5 % by weight.
According to the lithium battery of embodiment of the present invention, described hydroxyl material is aromatic substances.
According to the lithium battery of embodiment of the present invention, described hydroxyl material is for being selected from following formula (2-1) at least one compound to formula (2-4):
According to the lithium battery of embodiment of the present invention, described hydroxyl material is non-aromatic material.
According to the lithium battery of embodiment of the present invention, described hydroxyl material is for being selected from following formula (3-1) at least one compound to formula (3-4):
Wherein, the n in formula (3-2) and formula (3-3) is respectively 0～30.
According to the lithium battery of embodiment of the present invention, the described compound based on maleimide can be for example the copolymer of maleimide, bismaleimides, poly maleimide, polybismaleimide, bismaleimides and maleimide or the mixture of above-mentioned substance.
According to the lithium battery of embodiment of the present invention, described additive further comprises vinylene carbonate.
According to the lithium battery of embodiment of the present invention, further comprise the encapsulating structure for packing anode, negative electrode, barrier film and electrolyte solution.
The present invention also proposes lithium battery manufacture method, and it comprises the following steps., under the environment of-5 DEG C to 15 DEG C, with barrier film, anode and negative electrode separated and make battery utmost point volume at dew point, its Anodic, negative electrode and barrier film limit holding area jointly.In holding area, add electrolyte solution, wherein electrolyte solution comprises organic solvent, lithium salts and additive, and additive comprises the compound based on maleimide.
According to the lithium battery manufacture method of embodiment of the present invention, the described step that adds electrolyte solution in holding area is directly after making battery utmost point volume, to carry out.
According to the lithium battery manufacture method of embodiment of the present invention, described additive further comprises the hydroxyl material that molecular weight is less than 1000.
According to the lithium battery manufacture method of embodiment of the present invention, described additive further comprises vinylene carbonate.
According to the lithium battery manufacture method of embodiment of the present invention, it further comprises packs anode, negative electrode, barrier film and electrolyte solution with encapsulating structure.
According to the lithium battery manufacture method of embodiment of the present invention, the final water content in described electrolyte solution is 50ppm to 500ppm.
Based on foregoing, lithium battery of the present invention is by the contained compound based on maleimide and hydroxyl material in the additive package in electrolyte solution, make to produce in additive package electrochemical reaction, and form particular matter at electrode surface, to slow down the decomposition of electrolyte solution on electrode surface.Therefore, can reduce the loss of capacitance of lithium battery in the time of charge and discharge cycles, and effectively improve capacitance and improve battery behavior.
In addition, lithium battery manufacture method of the present invention can solve the problem of high water content in known lithium battery, and need under high aridity low water content environment, not carry out manufacturing technology steps.Therefore, can effectively reduce manufacturing cost and improve battery performance.
For above-mentioned feature and advantage of the present invention are become apparent, be hereinafter illustrated with experimental example, and elaborate with reference to accompanying drawing.
Brief description of the drawings
Fig. 1 is according to the generalized section of the lithium battery of one embodiment of the present invention.
Fig. 2 is the local enlarged diagram of the part A of Fig. 1.
Fig. 3 is the manufacturing step flow chart according to the lithium battery of one embodiment of the present invention.
Fig. 4 shows the charging and discharging cycle-index of lithium battery of experimental example of the present invention and comparative example and the graph of relation of battery capacity.
Fig. 5 shows that the lithium battery of experimental example of the present invention and comparative example carries out AC impedance (AC impedance) collection of illustrative plates in charging process.
Main element symbol description
100: lithium battery
102: anode
102a: Copper Foil
102b: anode active material
104: negative electrode
106: barrier film
108: electrolyte solution
110: holding area
112: encapsulating structure
202: solid electrolyte interface
S302, S304, S306: step
A: part
Embodiment
Fig. 1 is according to the generalized section of the lithium battery of one embodiment of the present invention.With reference to Fig. 1, lithium battery 100 comprises anode 102, negative electrode 104, barrier film 106 and electrolyte solution 108.Negative electrode 104 is relative with anode 102, and barrier film 106 is between anode 102 and negative electrode 104.Anode 102, negative electrode 104 and the common holding area 110 that limits of barrier film 106.Electrolyte solution 108 is arranged in holding area 110.In addition, lithium battery 100 further comprises outer enclosure structure 112, and this encapsulating structure 112 is conventionally known aluminum foil sealing pack, and it is for packing anode 102, negative electrode 104, barrier film 106 and electrolyte solution 108.
Anode 102 comprises Copper Foil 102a and anode active material 102b, and anode active material 102b coating or sputter are on Copper Foil 102a.Anode active material 102b can be LiAl, LiZn, Li
3bi, Li
3cd, Li
3sb, Li
4si, Li
4.4pb, Li
4.4sn, LiC
6, Li
3feN
2, Li
2.6co
0.4n, Li
2.6cu
0.4the combination of N or above-mentioned substance.Meanwhile, anode active material 102b also can be the mixture of carbon dust, graphite, carbon fiber, carbon nano-tube or above-mentioned substance.In one embodiment, anode active material 102b is the approximately carbon dust between 5 μ m to 30 μ m of particle diameter.Except above-mentioned substance, anode active material 102b can further comprise metal oxide as SnO, SnO
2, GeO, GeO
2, In
2o, In
2o
3, PbO, PbO
2, Pb
2o
3, Pb
3o
4, Ag
2o, AgO, Ag
2o
3, Sb
2o
3, Sb
2o
4, Sb
2o
5, SiO, ZnO, CoO, NiO, FeO or above-mentioned substance combination.
The material of above-mentioned negative electrode 104 can be for example lithium-composite oxide of metal (lithium-metal composite oxide), and it can be LiMnO
2, LiMn
2o
4, LiCoO
2, Li
2cr
2o
7, Li
2crO
4, LiNiO
2, LiFeO
2, LiNixCo
1-xo
2, LiFePO
4, LiMn
xni
yo
2, LiMn
xco
yni
zo
2, LiMc
0.5mn
1.5o
4, or the combination of above-mentioned substance, wherein 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z sum is 1, and Mc is divalent metal.
In addition, in one embodiment, above-mentioned anode 102 and/or negative electrode 104 can further have the polymer adhesive (polymer binder) for increasing the engineering properties of electrode.Suitable polymer adhesive can be Kynoar (polyvinylidene fluoride, be called for short PVDF), the composition of styrene butadiene ribber (styrene-butadiene rubber, be called for short SBR), polyamide (polyamide), melmac (melamine resin) or above-mentioned substance.
Barrier film 106 can comprise insulating material, and it can be for example that the multi-layer compound structure of polyethylene (polyethylene, PE), polypropylene (polypropylene, PP) or above-mentioned material is as PE/PP/PE.
The main component of electrolyte solution 108 is organic solvent, lithium salts and additive, wherein the addition of organic solvent accounts for 60～50 % by weight of electrolyte solution 108, the addition of lithium salts accounts for 35～50 % by weight of electrolyte solution 108, and the addition of additive accounts for 0.05～5 % by weight of electrolyte solution 108.Organic solvent can be gamma-butyrolacton (γ-butyrolactone, GBL), ethylene carbonate (ethylene carbonate, EC), propene carbonate (propylene carbonate, PC), diethyl carbonate (diethyl carbonate, DEC), propyl acetate (propyl acetate, PA), dimethyl carbonate (dimethyl carbonate, DMC), the combination of methyl ethyl carbonate (ethylmethyl carbonate, EMC) or above-mentioned substance.Lithium salts can be LiPF
6, LiBF
4, LiAsF
6, LiSbF
6, LiClO
4, LiAlCl
4, LiGaCl
4, LiNO
3, LiC (SO
2cF
3)
3, LiN (SO
2cF
3)
2, LiSCN, LiO
3sCF
2cF
3, LiC
6f
5sO
3, LiO
2cCF
3, LiSO
3f, LiB (C
6h
5)
4, LiCF
3sO
3, or the combination of above-mentioned substance.
Additive in electrolyte solution 108 comprises the compound based on maleimide (maleimide), material and the vinylene carbonate of hydroxyl (hydroxy group), and wherein the molecular weight of hydroxyl material is less than 1000.The content of compound based on maleimide in electrolyte solution 108 can be for example approximately 0.05 % by weight to 5 % by weight.The content of hydroxyl material in electrolyte solution 108 can be for example approximately 0.05 % by weight to 5 % by weight.The content of vinylene carbonate in electrolyte solution 108 can be for example approximately 0 % by weight to 2 % by weight.
The compound based on maleimide in additive can be for example copolymer of maleimide, bismaleimides, poly maleimide, polybismaleimide, bismaleimides and maleimide or the mixture of above-mentioned substance.Maleimide can be for example N-phenylmaleimide, N-(o-methyl-phenyl-)-maleimide, N-(aminomethyl phenyl)-maleimide, N-(p-methylphenyl)-maleimide, N-N-cyclohexylmaleimide, maleimide amino phenols, the amino benzocyclobutene of maleimide, phosphorous maleimide, phosphate maleimide, siloxy group maleimide, N-(THP trtrahydropyranyl-oxygen base phenyl) maleimide or 2,6-xylyl maleimide.The structural formula of bismaleimides is as shown in the formula shown in (1-1):
R in above-mentioned formula (1-1) can be
From the above, in additive, molecular weight is less than 1000 hydroxyl material and can be aromatic substances or non-aromatic material.Particularly, in the time that hydroxyl material is aromatic substances, hydroxyl material can be and is selected from following formula (2-1) at least one compound to formula (2-4):
In the time that hydroxyl material is non-aromatic material, hydroxyl material can be and is selected from following formula (3-1) at least one compound to formula (3-4):
Wherein, the n in formula (3-2) and formula (3-3) is respectively 0～30.In addition,, in execution mode, in the time that the additive in electrolyte solution 108 comprises suc as formula water shown in (3-1), the final water content in electrolyte solution 108 is about 50ppm to 500ppm.
What specify is, embodiment of the present invention utilize compound based on maleimide and certain content hydroxyl material (as water or other have can water absorbing functional groups molecule) as the additive package of electrolyte solution 108, therefore can contribute to improve capacitance and the cycle life of lithium battery.Particularly, in the additive of electrolyte solution 108, compound, hydroxyl material and vinylene carbonate based on maleimide can carry out each other coupling electrochemical reaction (coupling electrochemical reaction) and form particular matter at anode surface, be solid electrolyte interface (solid electrolyte interface, SEI).
Fig. 2 is the local enlarged diagram of the part A of Fig. 1.For example, as shown in Figure 2, because the compound based on maleimide, hydroxyl material and the vinylene carbonate of the additive in electrolyte solution 108 can carry out electrochemical reaction, therefore can on anode 102 surfaces that contact with electrolyte solution 108, (being on carbide 102b) form solid electrolyte interface 202.Thus, can utilize solid electrolyte interface 202 to slow down the lip-deep further decomposition of electrolyte solution 108 at anode 102, thereby improve the efficiency for charge-discharge of anode 102, and reduce the irreversible loss of capacitance of charging and discharging lithium battery circulation time.
In addition, although above-mentioned execution mode taking formula (2-1) to the aromatic compounds shown in formula (2-4) and formula (3-1) describe to the non-aromatic compound shown in formula (3-4) as example, the present invention is not limited to this.Those of ordinary skill in the art can be according to product demand and process conditions; adjust voluntarily the contamination of the hydroxyl material of additive in electrolyte solution 108; as long as make the molecular weight of hydroxyl material be less than 1000 and content in electrolyte solution be about 0.05 % by weight to 5 % by weight, be the scope that the present invention protects.
Next by the manufacture method of explanation lithium battery.It is noted that, following flow process is mainly that the manufacture method in order to describe lithium battery of the present invention in detail can be carried out under the atmospheric environment of low aridity or general aridity, so that those skilled in the art can implement according to this, but not in order to limit scope of the present invention.About material, constituent, generation type and the order of other member of lithium battery, the fabrication techniques that all can know according to those of ordinary skill in the art, or realize according to aforementioned embodiments, and be not limited to described in following execution mode.Fig. 3 is the manufacturing step flow chart according to the lithium battery of an embodiment of the invention.
With reference to Fig. 3, carry out step S302,, under the environment of-5 DEG C to 15 DEG C, with barrier film, anode and negative electrode separated and make battery utmost point volume at dew point, its Anodic, negative electrode and barrier film limit holding area jointly.In addition,, before carrying out step S302, can first carry out the preparation of anode and negative electrode.Afterwards, can, at dew point under the atmospheric environment of the low aridity of-5 DEG C to 15 DEG C or general aridity, use PP as barrier film, and be made into battery utmost point volume after anode and negative electrode being separated by the mode of reeling.The relative humidity of the atmospheric environment of above-mentioned low aridity or general aridity can be for example approximately 15% to 50%.In one embodiment, this battery utmost point volume does not need to be placed on for a long time under atmospheric environment, can directly carry out subsequent technique.In another embodiment, battery utmost point volume also can first be placed under atmospheric environment after length, just carries out subsequent technique.
Carry out step S304, add electrolyte solution in holding area, wherein electrolyte solution comprises organic solvent, lithium salts and additive, and additive comprises compound and vinylene carbonate based on maleimide.Can be for example by organic solvent, lithium salts and additive be mixed and prepare electrolyte solution, wherein the addition of organic solvent accounts for 60～50 % by weight of electrolyte solution, the addition of lithium salts accounts for 35～50 % by weight of electrolyte solution, and the addition of additive accounts for 0.05～5 % by weight of electrolyte solution.In addition, in one embodiment, the additive that pours into the electrolyte solution in holding area further comprises hydroxyl material, and the molecular weight of hydroxyl material is less than 1000.Described herein, kind, the content etc. of hydroxyl material can be adjusted according to aforementioned embodiments, change and apply, therefore do not repeat them here.
Carry out step S306, pack anode, negative electrode, barrier film and electrolyte solution with encapsulating structure, thereby complete the making of lithium battery structure.
What specify is, by carry out the making of lithium battery under specific damp condition, can utilize the water (moisture) in environment to carry out coupling electrochemical reaction with the additive in electrolyte solution, and on electrode surface, form solid electrolyte interface, thereby can reach as described in the embodiment add the effect of hydroxyl material as the additive of electrolyte solution.And, generally well-known technology must be carried out manufacturing process before encapsulation lithium battery under the environment of high aridity low water content, but the manufacture method of lithium battery of the present invention can be carried out processing step at dew point under the atmospheric environment of the low aridity of-5 DEG C to 15 DEG C or general aridity, and need under the environment of high aridity low water content, not carry out, also need not carry out strict dry processing, therefore in effectively improving lithium battery capacity and battery performance, also can further reduce cost of manufacture.
For confirming really there is for lithium battery and the manufacture method thereof of embodiment of the present invention the effect that improves battery performance, next will its characteristic be described with experimental example.The data result of following experimental example is only used for illustrating the characteristics such as battery capacity, battery efficiency and the AC impedance of the produced lithium battery of embodiment of the present invention, and is not to limit scope of the present invention.
Experimental example
By the LiCoO of 90 weight portions
2, 5 weight portions Kynoar (polyvinylidene difluoride, PVDF) and the acetylene black of 5 weight portions (conducting powder) be scattered in 1-METHYLPYRROLIDONE (N-methyl-2-pyrrolidinone, NMP) in, this slurry is coated on aluminium foil, be dried afterwards, compress and cut out to form negative electrode.In addition, the PVDF of the graphite of 95 weight portions and 5 weight portions is scattered in NMP, this slurry is coated on aluminium foil, be dried afterwards, compress and cut out to form anode.Then, at dew point under the low aridity of-5 DEG C to 15 DEG C or general aridity atmospheric environment, use PP as barrier film, after anode and negative electrode being separated by winding method, be made into battery utmost point volume, and be placed on lower six months of the atmospheric environment of general humidity or high humility (as relative humidity > 95%).
Afterwards, mix propene carbonate (the propylene carbonate of 2 parts by volume, PC), the ethylene carbonate of 3 parts by volume (ethylene carbonate, EC) and the diethyl carbonate of 5 parts by volume (diethyl carbonate, DEC) as the organic solvent of electrolyte solution.The lithium salts of electrolyte solution is LiPF
6, concentration is 1M.The additive of electrolyte solution is bismaleimides and vinylene carbonate, wherein the structure of bismaleimides is suc as formula shown in (1-2), and the addition of bismaleimides accounts for 0.1 % by weight of electrolyte solution, the addition of vinylene carbonate accounts for 2 % by weight of electrolyte solution.Afterwards, in the holding area between anode and negative electrode, add above-mentioned electrolyte solution.Finally seal said structure with encapsulating structure, thereby complete the manufacture of lithium battery, and carry out battery charging and discharging test under general room temperature.In the lithium battery of experimental example manufacturing, the final water content in electrolyte solution is about 500ppm.
Comparative example
By the LiCoO of 90 weight portions
2, the PVDF of 5 weight portions and the acetylene black (conducting powder) of 5 weight portions is scattered in 1-METHYLPYRROLIDONE (NMP), and this slurry is coated on aluminium foil, is dried afterwards, compress and cut out to form negative electrode.In addition, the PVDF of the graphite of 95 weight portions and 5 weight portions is scattered in NMP, this slurry is coated on aluminium foil, be dried afterwards, compress and cut out to form anode.Then, at dew point under the atmospheric environment of the high aridity of-25 DEG C to-40 DEG C, using PP as barrier film, and be made into battery utmost point volume after anode and negative electrode being separated by winding method, and be placed on lower six months of the atmospheric environment of high aridity (as relative humidity < 5%).Afterwards, complete the making of lithium battery with the method identical with above-mentioned experimental example, and carry out battery charging and discharging test under general room temperature.
In other words, in comparative example, except making battery utmost point volume under the atmospheric environment at high aridity (as relative humidity < 5%), and outside lower six months of the atmospheric environment that is placed on high aridity, kind and the ratio of the production method of other battery, the organic solvent of electrolyte solution, lithium salts, additive are all manufactured lithium battery in the mode identical with above-mentioned experimental example.
Electrical property is measured
A. battery capacity:
The lithium battery of experimental example and comparative example is carried out to charging and discharging with fixed current/voltage.First, with 0.2mA/cm
2fixed current battery is charged to 4.2V, until electric current is less than or equal to 0.1mA.Then, then by battery with fixed current 0.2mA/cm
2be discharged to cut-ff voltage (2.75V).Battery capacity (mAh) and the battery efficiency (efficiency) of experimental example and comparative example are as shown in table 1 below.
B. charging and discharging loop test:
The lithium battery of experimental example and comparative example is carried out to charging and discharging with fixed current/voltage.First, with the fixed current of 260mA, battery is charged to 4.2V, until electric current is less than or equal to 2.6mA.Then, then by battery with fixed current 1mA/cm
2be discharged to cut-ff voltage (2.75V), and repeat said process 7 times.The battery capacity (mAh) of experimental example and comparative example is as shown in table 1.In addition, Fig. 4 shows the charging and discharging cycle-index of lithium battery of experimental example of the present invention and comparative example and the graph of relation of battery capacity.
C. AC impedance test:
The lithium battery of experimental example and comparative example is carried out, after the 7th electric discharge completely of taking turns, utilizing the AC wave that amplitude is 5mV with fixed current, and carrying out frequency separation is the two electrode AC impedance scannings of 100K～0.01Hz.
Fig. 5 shows that the lithium battery of experimental example of the present invention and comparative example carries out the ac impedance spectroscopy in charging process.
Table 1
As shown in Table 1, experimental example of the present invention is in the time comparing with comparative example, and after circulation 7 times, the battery capacity of experimental example increases approximately 5%～10%.In addition, as shown in the result of Fig. 4, not withering experimental example is placed the cycle life that exceedes 6 months high humility (as relative humidity > 95%) in external environment, higher than the strict dry cycle life of processing and being placed on for a long time the comparative example under high aridity (as relative humidity < 5%) environment of warp.Although compared with comparative example, the electrical property irreversibility poor and cell reaction that the lithium battery of experimental example discharged and recharged in the first round is larger, this is mainly because experimental example is in the time that the first round discharges and recharges, additive in electrolyte solution and water carry out electrochemical reaction, and on electrode surface, form solid electrolyte interface (as shown in Figure 2).But after second takes turns charge and discharge cycles, the battery capacity of experimental example is apparently higher than the battery capacity of comparative example.Hence one can see that, and the lithium battery of experimental example of the present invention can be by being placed in the environment having under certain humidity, and its integral battery door capacitance approximately can improve 5%～10% as calculated.
In addition, as shown in Figure 5, along with the carrying out of lithium cell charging, the ascensional range of the AC impedance of the lithium battery of experimental example is much smaller than the lithium battery of comparative example, and the integral battery door AC impedance of the lithium battery of experimental example is also lower than the lithium battery of comparative example, and therefore the cycle life of the lithium battery to experimental example has the effect of gain.
From above-mentioned data, by lithium battery of the present invention and manufacture method thereof, even without super-dry processing, still can effectively improve the lithium battery capacity of lithium battery.Thus, do not needing to change under the situation of any battery design and electrode material, the electrochemical reaction that can be undertaken by the additive of electrolyte solution, reaches effect of improving battery capacity and efficiency.
In sum, lithium battery of the present invention and manufacture method thereof at least have following advantages:
1. in the lithium battery of above-mentioned experimental example, utilize compound based on maleimide and hydroxyl material as the additive package of electrolyte solution, can effectively improve battery capacity and efficiency.
2. the manufacture method of the lithium battery of above-mentioned experimental example, can, by carry out the making of lithium battery under specific damp condition, make the water in environment to produce electrochemical reaction with additive, thereby can contribute to promote the capacitance of lithium battery.
3. the lithium battery of above-mentioned experimental example and manufacture method thereof can be integrated mutually with existing manufacturing process, its manufacturing process, formula simply even do not need high-accuracy dry factory building, can effectively improve battery performance, therefore can significantly reduce battery cost of manufacture and promote inter-industry competition.
Although the present invention discloses as above with experimental example; but it is not in order to limit the present invention; any those of ordinary skill in the art without departing from the spirit and scope of the present invention, can improve and modification, and protection scope of the present invention is defined by the following claims.
Claims (7)
1. lithium battery, comprising:
Anode;
The negative electrode relative with described anode;
Barrier film between described anode and described negative electrode, wherein said anode, described negative electrode and described barrier film limit holding area jointly; And
Be arranged in the electrolyte solution of described holding area, wherein said electrolyte solution comprises organic solvent, lithium salts and additive, and described additive comprises:
Based on the compound of maleimide; And
The hydroxyl material that molecular weight is less than 1000, and the content of described hydroxyl material in described electrolyte solution is 0.05 % by weight to 5 % by weight,
Wherein said hydroxyl material is for being selected from following formula (2-1) at least one aromatic substances to formula (2-3):
Or described hydroxyl material is for being selected from following formula (3-1) at least one non-aromatic material to formula (3-4):
Wherein, the n in formula (3-2) and formula (3-3) is respectively 0～30.
2. the lithium battery of claim 1, the wherein said compound based on maleimide comprises the copolymer of maleimide, bismaleimides, poly maleimide, polybismaleimide, bismaleimides and maleimide or the mixture of above-mentioned substance.
3. the lithium battery of claim 1, further comprises the encapsulating structure for packing described anode, described negative electrode, described barrier film and described electrolyte solution.
4. the manufacture method of lithium battery, comprising:
, under the environment of-5 DEG C to 15 DEG C, with barrier film, anode and negative electrode separated and make battery utmost point volume at dew point, wherein said anode, described negative electrode and described barrier film limit holding area jointly; And
In described holding area, add electrolyte solution, wherein said electrolyte solution comprises organic solvent, lithium salts and additive, and described additive comprises the compound based on maleimide,
Described additive further comprises the hydroxyl material that molecular weight is less than 1000, and wherein said hydroxyl material is for being selected from following formula (2-1) at least one aromatic substances to formula (2-3):
Or described hydroxyl material is for being selected from following formula (3-1) at least one non-aromatic material to formula (3-4):
Wherein, the n in formula (3-2) and formula (3-3) is respectively 0～30.
5. the manufacture method of the lithium battery of claim 4, the step that wherein adds described electrolyte solution in described holding area is directly after making described battery utmost point volume, to carry out.
6. the manufacture method of the lithium battery of claim 4, further comprises and packs described anode, described negative electrode, described barrier film and described electrolyte solution with encapsulating structure.
7. the manufacture method of the lithium battery of claim 4, the final water content in described electrolyte solution is 50ppm to 500ppm.
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| CN110165320B (en) * | 2019-06-17 | 2021-07-30 | 商丘神风能源科技有限公司 | Quick charging method based on high-temperature-resistant lithium ion battery |
| CN111554969A (en) * | 2020-06-19 | 2020-08-18 | 中节能万润股份有限公司 | Lithium ion battery electrolyte additive containing sulfonic acid phosphonium salt, preparation method and application thereof |
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| CN1757130A (en) * | 2003-03-06 | 2006-04-05 | 东丽株式会社 | Polymer electrolyte material, polymer electrolyte part, film electrode composite element and polymer electrolyte fuel cells |
| TW200926479A (en) * | 2007-12-03 | 2009-06-16 | Ind Tech Res Inst | Electrolytic solution and lithium battery employing the same |
| TW201001781A (en) * | 2008-06-17 | 2010-01-01 | Ind Tech Res Inst | Lithium battery |
| TW201015767A (en) * | 2008-10-03 | 2010-04-16 | Ind Tech Res Inst | Positive electrode and method for manufacturing the same and lithium battery utilizing the same |
| CN101841061A (en) * | 2010-05-10 | 2010-09-22 | 陈韵吉 | Low-temperature electrolyte of lithium iron phosphate power battery and preparation method thereof |
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| CN1757130A (en) * | 2003-03-06 | 2006-04-05 | 东丽株式会社 | Polymer electrolyte material, polymer electrolyte part, film electrode composite element and polymer electrolyte fuel cells |
| TW200926479A (en) * | 2007-12-03 | 2009-06-16 | Ind Tech Res Inst | Electrolytic solution and lithium battery employing the same |
| TW201001781A (en) * | 2008-06-17 | 2010-01-01 | Ind Tech Res Inst | Lithium battery |
| TW201015767A (en) * | 2008-10-03 | 2010-04-16 | Ind Tech Res Inst | Positive electrode and method for manufacturing the same and lithium battery utilizing the same |
| CN101841061A (en) * | 2010-05-10 | 2010-09-22 | 陈韵吉 | Low-temperature electrolyte of lithium iron phosphate power battery and preparation method thereof |
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