CN101212065A - Non-aqueous electrolyte containing maleimide admixture and alkali metal secondary battery containing the non-aqueous electrolyte - Google Patents
Non-aqueous electrolyte containing maleimide admixture and alkali metal secondary battery containing the non-aqueous electrolyte Download PDFInfo
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- CN101212065A CN101212065A CNA2006101723145A CN200610172314A CN101212065A CN 101212065 A CN101212065 A CN 101212065A CN A2006101723145 A CNA2006101723145 A CN A2006101723145A CN 200610172314 A CN200610172314 A CN 200610172314A CN 101212065 A CN101212065 A CN 101212065A
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Abstract
The invention relates to non-water electrolyte comprising an additive of maleimide and a secondary battery comprising the non-water electrolyte. The non-water electrolyte comprising an additive of maleimide comprises: an electrolyte of alkali salt; a nonaqueous solvent and an additive comprising maleimide, wherein, the additive comprising maleimide comprises a maleimide, a second maleimide, an oligomer of the second maleimide and a combination thereof.
Description
Technical field
The present invention is about a kind of electrolyte and comprise its secondary cell, more specifically, and the secondary cell that the present invention relates to contain the nonaqueous electrolytic solution of maleimide additive and comprise it.
Background technology
Along with the direction of portable electronic product towards " light, thin, short, little " develops, the electronics spare part is gradually miniaturization also, and is especially urgent to the high-performance secondary cell demand that volume is little, in light weight, energy density is high.Many as camera, mobile phone, mobile computer, electric motor car and electric power stocking system products such as (as UPSs), all do one's utmost demand in wireless penetration, can taking (portable) and multifunction, in the power supply supply, require long, in light weight, stability and safe service time especially.
In addition, the new line of environmental consciousness, various application products will be required to use the green material of unleaded without phosphorus Halogen, to avoid causing environmental pollution and greenhouse effect.Therefore the clear energy sources problem that may face in the face of 21st century, the exploitation of novel battery will be played the part of very important role, and the battery of researching and developing a kind of high-performance, high-energy-density and meeting environmental protection needs is to become the actively problem of input of each advanced country.
The secondary cell of rechargeable type promptly arises at the historic moment under the driving of this demand, and especially lithium battery is owing to have advantages such as voltage height, energy density height and holding time length, and the utmost point is subjected to the attention of all circles.Lithium rechargeable battery since Japanese Sony Energy Tech company releases, has just had breakthrough growth always; Because of it has the voltage that is higher than 3 times of Ni-MH batteries, and characteristics such as high-output power, quickly-chargeable, long circulation life and discharge be steady, though still high on price, and on safety, also have a misgiving; But, hold its absolute predominance on energy density under the arm, development in future has suitable potentiality.Research and development and improvement at secondary cell, several directions are arranged at present, comprise the capacitance that enhances battery, discharge and recharge usefulness, life-span circulation, electrochemical stability, thermal stability and flame resistance, and safe function etc., except from the selection assembly and improvement of pole plate positive and negative pole material or barrier film, the most direct and effective method is to be set about by its electrolyte, and electrolyte mainly is divided into lithium salts, transmits dielectric solvent system two parts.
Desirable electrolyte must have high-k and low viscous characteristic simultaneously, and therefore general electrolyte can contain the cyclic carbonates and the low viscous linear carbonate class of high-k simultaneously.The normal use of institute in the industry cycle at present comprises the electrolyte of ethylene carbonate and propylene carbonate, and its voltage can reach 3.6V, and energy density also can reach 250～300Wh/L (or 90～110Wh/kg); But, because ethylene carbonate (Ethylene Carbonate, EC) be the solvent of fusing point up to 37 degree Celsius, cause the battery efficiency of battery under low-temperature condition not good, and propylene carbonate (Propylene Carbonate, PC) then easy and lithium ion produces " moving into altogether " (co-intercalation) effect, can enter carbon material negative pole inside, when current potential reaches the reduction potential of PC, PC can produce reductive cleavage, can generate the destruction that gas causes negative pole structure simultaneously, so in the electrolyte during too high levels of PC, tend to cause the minimizing of battery life.In addition, so the electrolyte system of ethylene carbonate and propylene carbonate combination, still have thermal stability and flame resistance, and problem such as safe function exists; Therefore how to maintain the battery performance after discharging and recharging, simultaneously can have good high low temperature life-span circulation usefulness, electrochemical stability, wetability, thermal stability, flame resistance concurrently, and safe function etc., all are the problems that in electrolyte, import the required solution of additive and overcome.
The electrolyte system of general commercial ethylene carbonate and propylene carbonate combination, except the usefulness of proportioning of adjusting solvent composition with the raising battery, often add such as dimethyl carbonate (DimethylCarbonate, DMC), diethyl carbonate (Diehtyl Carbonate, DEC) and methyl ethyl carbonate (EthylMethyl Carbonate, EMC), carbonic acid ethenylidene ester (Vinylene Carbonate), sulfurous esters (sulfites), sulfuric acid ester (sulfates), additives such as phosphate or derivatives thereof compound are in order to promote and to improve battery life, capacitance and low temperature usefulness; But the gain effect on the battery electrical property efficiency is still very limited, and in high temperature service life circulation usefulness, thermal stability, flame resistance, and aspect such as safe function also has many problems of failing to solve and overcoming to exist.
In view of this, the present invention discloses a kind of non-aqueous electrolyte that contains polyfunctional group maleimide additive, function and performance in order to the non-aqueous electrolyte that can improve and promote secondary cell in all directions, the utilization level of secondary cell is improved, solves the problem that existing electrolyte is met with.
Summary of the invention
The present invention's purpose is to provide a kind of secondary cell that contains the nonaqueous electrolytic solution of maleimide additive and comprise it.The two keys of the maleimide of this maleimide additive internal memory, phenyl (phenyl), carbonyl (carboxyl) and imido grpup functional groups (functional groups) such as (imide); can improve and promote the function and the performance of the non-aqueous electrolyte of secondary cell; comprise discharging and recharging usefulness, life-span circulation, electrochemical stability, thermal stability and flame resistance, and the protection function that overcharges etc.
For reaching above-mentioned purpose, the nonaqueous electrolytic solution that contains the maleimide additive of the present invention is to be used for alkali metal family secondary cell, comprises:
The electrolyte of alkali metal salt;
Nonaqueous solvents; And
Contain the maleimide additive, wherein this contains the maleimide additive and comprises maleimide, dimaleimide, bismaleimide oligomer or its combination.
In addition, the present invention also provides alkali metal family secondary cell, except comprising above-mentioned electrolyte, more comprises positive pole and negative pole; And barrier film, be located between this positive pole and this negative pole.
Description of drawings
The 1st and 2 figure system shows that respectively the electrolyte of Comparative Examples 1 of the present invention and embodiment 1～embodiment 5 discharges and recharges usefulness (R.T.cycle).
Embodiment
Below by several embodiment and Comparative Examples and in conjunction with the accompanying drawings, with feature and the advantage that illustrates further method of the present invention, but be not to be used for limiting the scope of the invention, scope of the present invention should be as the criterion with appended claims.
Alkali metal provided by the present invention family secondary cell, the nonaqueous electrolytic solution that comprises positive pole, negative pole, is located at the barrier film between this positive pole and this negative pole and has safety additives.
Alkali metal provided by the present invention family secondary cell, the nonaqueous electrolytic solution that comprises positive pole, negative pole, is located at the barrier film between this positive pole and this negative pole and contains the maleimide additive.
The nonaqueous electrolytic solution that contains the maleimide additive
The nonaqueous electrolytic solution that contains the maleimide additive of the present invention comprises: the electrolyte of alkali metal salt; Nonaqueous solvents; And, the maleimide additive.
The alkali metal salt electrolyte that the present invention was suitable for comprises 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), LiSCN, LiO
3SCF
2CF
3, LiC
6F
5SO
3, LiO
2CCF
3, LiSO
3F, LiB (C
6H
5), LiCF
3SO
3Or its combination.
The nonaqueous solvents that the present invention was suitable for can be aprotic solvent, optional free ethylene carbonate, propylene carbonate, butylene carbonate (butylene carbonate), dipropyl carbonate (dipropyl carbonate), acid anhydrides (acid anhydride), N-methyl pyrrolidone (N-methyl pyrrolidone), N-methylacetamide (N-methyl acetamide), N-methylformamide (N-methyl formamide), dimethyl formamide (dimethyl formamide), diethylformamide (diethoxyethane, DEE), γ-butyl lactone (γ-butyrolactone), acetonitrile (acetonitrile), methyl-sulfoxide (dimethyl sulfoxide), dimethyl sulfite (dimethyl sulfite), vinylene carbonate (vinylene carbonate, VC), carbonic acid first propyl ester propyl methyl carbonate (PMC), 1,3-dioxolanes (1,3-dioxolane), 1,2-diethoxyethane (1,2-diethoxyethane), 1,2 dimethoxy-ethanes (1,2-dimethoxyethane), 1,2-dibutoxy ethane (1,2-dibutoxyethane), oxolane (tetrahydrofuran), 2-methyltetrahydrofuran (2-methyl tetrahydrofuran), expoxy propane (propylene oxide), methyl acetate (methylacetate), ethyl acetate (ethyl acetate), methyl butyrate (methyl butyrate), ethyl butyrate (ethylbutyrate), methyl propionate (methyl proionate), ethyl propionate (ethyl proionate), dimethyl carbonate, diethyl carbonate (Diethyl Carbonate, DEC), methyl ethyl carbonate (Ethyl MethylCarbonate, EMC), propyl acetate (Propyl acetate, PA) group of Zu Chenging.
Maleimide additive of the present invention can comprise maleimide, dimaleimide, bismaleimide oligomer or its combination.It should be noted that this adding proportion that contains the maleimide additive accounts for 0.01%～10% of electrolyte weight percentage, is preferably 0.1%～5%.
This maleimide can have structure shown in formula (I) and the formula (II):
Formula (I) formula (II)
R wherein
1Can be-RCH
2-(alkyl) ,-RNH
2R ,-C (O) CH
3,-CH
2OCH
3,-CH
2S (O) CH
3,-C
6H
5,-CH
2(C
6H
5) CH
3, stretch phenyl, stretch xenyl, cyclic aliphatic, or the aromatic series of silane substituted; Y can be-H ,-R ,-RCH
3,-C (CH
3)
3, or-S (O)-R ,-CONH
2,-C (CF
3)
3Deng; R
2Be H independently, F, Cl, Br, HSO
3, SO
2Or has an alkyl of 1-6 carbon; And, R is the alkyl of 1-6 carbon, and for example optional free maleimide-phenyl is for methane (maleimide-phenylmethane), phenyl maleimide (phenyl-maleimide), tolyl maleimide (methylphenyl maleimide), 3,5-dimethylphenyl maleimide [dimethylphenyl-maleimide], vinyl maleimide (ethylenemaleimide), sulfo-maleimide (thio-maleimid), maleimide ketone (ketone-maleimid), methylene maleimide (methylene-maleinimid), maleimide methyl ether (maleinimidomethylether), dimaleoyl imino-ethylene glycol (maleimido-ethandiol), 4-phenylate-maleimide (4-phenylether-maleimid), the group that 4-maleimide-benzene sulfone (4-maleimido-phenylsulfone) is formed.
This dimaleimide cording has structure shown in formula (III) and the formula (IV):
Formula (III) formula (IV)
R wherein
3For-RCH
2-(alkyl) ,-RNH
2R-,-C (O) CH
2-,-CH
2OCH
2-,-C (O)-,-O-,-O-O-,-S-,-S-S-,-S (O)-,-CH
2S (O) CH
2-,-(O) S (O)-,-C
6H
5-,-CH
2(C
6H
5) CH
2-,-CH
2(C
6H
5) (O)-, stretch phenyl, stretch xenyl, the xenyl of stretching of stretching phenyl or replacement of replacement, and R
4For-RCH
2-,-C (O)-,-C (CH
3)
2-,-O-,-O-O-,-S-,-S-S-,-(O) S (O)-, or-S (O)-, for example optional free N, N '-dimaleimide-4,4 '-diphenyl is for methane (N, N '-bismaleimide-4,4 '-diphenylmethane), 1,1 '-(di-2-ethylhexylphosphine oxide-4, the 1-phenylene) dimaleimide [1,1 '-(methylenedi-4,1-phenylene) bismaleimide], N, N '-(1,1 '-diphenyl-4,4 '-dimethylene) dimaleimide [N, N '-(1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, N '-(4-methyl isophthalic acid, the 3-phenylene) dimaleimide [N, N '-(4-methyl-1,3-phenylene) bismaleimide], 1,1 '-(3,3 '-dimethyl-1,1 '-diphenyl-4,4 '-dimethylene) dimaleimide [1,1 '-(3,3 ' dimethyl-1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, and N '-vinyl dimaleimide (N, N '-ethylenedimaleimide), N, N '-(1, the 2-phenylene) dimaleimide [N, N '-(1,2-phenylene) dimaleimide], N, N '-(1, the 3-phenylene) dimaleimide [N, N '-(1,3-phenylene) dimaleimide], N, N '-dimaleimide sulphur (N, N '-thiodimaleimid), N, and N '-dimaleimide two sulphur (N, N '-dithiodimaleimid), N, N '-dimaleimide ketone (N, N '-ketonedimaleimid), N, and N '-methylene dimaleimide (N, N '-methylene-bis-maleinimid), dimaleimide first-ether (bis-maleinimidomethyl-ether), 1,2-dimaleimide base-1,2-ethylene glycol [1,2-bis-(maleimido)-1,2-ethandiol], N, N '-4,4 '-diphenyl ether-dimaleimide (N, N '-4,4 '-diphenylether-bis-maleimid), and 4,4 '-dimaleimide-diphenyl sulphone (DPS) (4,4 '-group of bis (maleimido)-diphenylsulfone) formed.
Bismaleimide oligomer of the present invention can be obtained by dimaleimide monomer and barbituric acid reaction, and wherein this dimaleimide monomer is above-mentioned dimaleimide, and this barbituric acid has structure shown in the formula (V):
Wherein, R
5And R
6Be identical or different substituting group, comprise H, CH
3, C
2H
5, C
6H
5, CH (CH
3)
2, CH
2CH (CH
3)
2, CH
2CH
2CH (CH
3)
2, or
This bismaleimide oligomer can be the polyfunctional group bismaleimide oligomer of high branched structure of a kind of tool (hyper branch architecture) or many pairs of key reactive functional groups (multi double bond reactive functional groups).Wherein this high branched structure (hyper branch architecture) mainly is to be structural matrix (architecture matrix) with the dimaleimide, on two keys of this barbituric acid with its free radical form grafting dimaleimide, make two keys of dimaleimide can open bilateral or one-sided, and the configuration organized polymerization that carries out collateralization (branching) and prefaceization (ordering) reacts, prop up a segmented structure in order to form, and lasting graft polymerization becomes high branched structure.In addition, this its segment of high branched structure is combined as-[(dimaleimide monomer)+(barbituric acid)
x]
m-, X is 0～4, be preferably 0.5～2.5, and number of repeat unit (repeating unit) m value is less than 20, preferably between 2～10.Moreover this high branched structure also can be branch kenel (branch type), and each branch is a segment, general branch's segment of high branched structure-{ [(dimaleimide)+(barbituric acid)
x]
m}
n-, wherein the ratio range of x is 0～4, most preferably be 0.5～2.5, and number of repeat unit (repeating unit) m value most preferably is 2～10 less than 20, and the repetitive n value of general branch's segment is less than 50, and most preferred range is 5～20.
In the preferred embodiment of the present invention, this nonaqueous electrolytic solution that contains the maleimide additive can further comprise surfactant, viscosity reductant or carbonate, for example lithium carbonate (Lithium carbonate), calcium carbonate (calcium carbonate) or magnesium carbonate (Magnesium carbonate).
The manufacturing of positive and negative electrode plate
Alkali metal of the present invention family secondary cell comprises positive pole and negative el.This positive electrical pole plate production method is as follows: anode sizing agent is that positive electrode active material, conductive additive 3-15% and the fluororesin adhesive 3-10% of 80-95% is dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP), then it is evenly coated aluminum foil coils long 300 meters, wide 35 centimeters, thick 20 μ m, dried anodal volume is bestowed spreading and itemize, at last it is spent vacuumizes 4 hours with Celsius 110.Positive electrode active material can be lithiumation oxide, lithiumation sulfide, lithiumation selenides and the lithiumation tellurides of metals such as vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt and manganese; The fluororesin adhesive is polyvinylidene fluoride (PVDF) for example; The conductivity activator can be carbon black, graphite, acetylene black, nickel powder, aluminium powder, titanium valve or stainless steel powder or the like.
In addition, this negative el production method is as follows: this cathode size then is dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP) with fluororesin adhesive 3-10% for the negative electrode active material 90% of diameter 1-30 μ m, coat aluminum foil coils long 300 meters, wide 35 centimeters, thick 10 μ m after stirring, formed negative pole volume is behind the spreading itemize, equally with 110 degree vacuumizes Celsius 4 hours.Negative electrode active material can be (for example: polyvinylidene fluoride) to be situated between surely mutually spherical carbon (MCMB), vapor deposition carbon fiber (VGCF), carbon nano-tube (CNT), coke, carbon black, graphite, acetylene black, carbon fiber and nature of glass carbon or fluororesin adhesive.
Barrier film
The present invention is owing to adopt the nonaqueous electrolytic solution that contains the tool safety additives, can be when battery be caused battery temperature to raise by improper use, produce chemical crosslink reaction apace, internal battery impedance is risen, reduce the conducting power of alkali metal family ion, improve the security feature of battery, therefore, can be the barrier film of conventional P P, PE, (PP/PE/PP) trilamellar membrane the selecting for use without limits of barrier film.
Below especially exemplified by embodiment and Comparative Examples, in order to the explanation the present invention, can be more clear in the hope of making the present invention:
The preparation of electrolyte
Comparative Examples 1:
Get the LiPF of 1.1M
6Be dissolved in ethylene carbonate (EC), propylene carbonate (PC) and the mixed solvent (volume ratio EC/PC/DEC=3/2/5) of diethyl carbonate (DEC), fully stir and make it even, and carry out de-bubble, do not add the maleimide additive that contains of the present invention.
Embodiment 1:
Get the LiPF of 1.1M
6Be dissolved in ethylene carbonate (EC), propylene carbonate (PC) and the mixed solvent (volume ratio EC/PC/DEC=3/2/5) of diethyl carbonate (DEC), the dimaleimide monomer that adds 0.1 percentage by weight is used as additive, fully stir and make it even, and carry out de-bubble.
Embodiment 2:
Get the LiPF of 1.1M
6Be dissolved in ethylene carbonate (EC), propylene carbonate (PC) and the mixed solvent (volume ratio EC/PC/DEC=3/2/5) of diethyl carbonate (DEC), the dimaleimide monomer that adds 0.5 percentage by weight is used as additive, fully stir and make it even, and carry out de-bubble.
Embodiment 3:
Get the LiPF of 1.1M
6Be dissolved in ethylene carbonate (EC), propylene carbonate (PC) and the mixed solvent (volume ratio EC/PC/DEC=3/2/5) of diethyl carbonate (DEC), the dimaleimide monomer that adds 1.0 percentage by weights is used as additive, fully stir and make it even, and carry out de-bubble.
Embodiment 4:
Get the LiPF of 1.1M
6Be dissolved in ethylene carbonate (EC), propylene carbonate (PC) and the mixed solvent (volume ratio EC/PC/DEC=3/2/5) of diethyl carbonate (DEC), the dimaleimide monomer that adds 5.0 percentage by weights is used as additive, fully stir and make it even, and carry out de-bubble.
Embodiment 5:
Get the LiPF of 1.1M
6Be dissolved in ethylene carbonate (EC), propylene carbonate (PC) and the mixed solvent (volume ratio EC/PC/DEC=3/2/5) of diethyl carbonate (DEC), the bismaleimide oligomer that adds 2.5 percentage by weights forms that (mol ratio of dimaleimide and barbituric acid is 10: 1, in 130 ℃ of down reactions 6 hours) be used as additive, fully stir and make it even, and carry out de-bubble.
Embodiment 6:
Get the LiPF of 1.1M
6Be dissolved in ethylene carbonate (EC), propylene carbonate (PC) and the mixed solvent (volume ratio EC/PC/DEC=3/2/5) of diethyl carbonate (DEC), the bismaleimide oligomer that adds 5.1 percentage by weights forms that (mol ratio of dimaleimide and barbituric acid is 10: 1, in 130 ℃ of down reactions 6 hours) be used as additive, fully stir and make it even, and carry out de-bubble.
The conductivity test
Nonaqueous electrolytic solution to Comparative Examples 1 and embodiment 6 gained carries out the conductivity test, and method is as follows:
The ionic conductance of electrolyte (σ) is tried to achieve with ac resistance analysis, passing under the situation of alternating current, sweeping (50000Hz) tremendously low frequency (100Hz) by high frequency scans, obtain the relation of each impedance and phase angle, and convert to true impedance (Z ') virtual impedance (the Nyquist figure of Z ") expression.Get the virtual impedance of ions diffusion curve (true impedance (Z ') intercept of Z ") when making zero, calculating formula is as follows:
σ＝L/A×R
σ=electrical conductivity
The distance (cm) of L=two interpolars
R=electrolyte impedance (Ω)
A=electrode area (cm
2)
The electrolyte electrical conductivity measures the design of groove: L=0.5cm; A=0.25 π cm
2
The conductivity test result is as shown in table 1.
Table 1: electrolyte impedance and ionic conductivity are relatively
As shown in Table 1, it is lower to have its impedance of nonaqueous electrolytic solution that contains the maleimide additive, and conductivity is higher.
Contain many not shared ion pair and polar functional base on the strand of the composition additive of bismaleimide oligomer and monomer, as-NH-,-CN,-C=O etc., easy and the lithium salts formation misfit body (Complex formation) of these structures, can promote the lithium ion conduction number effectively and promote ionic conductivity, can be verified by table one.The schematic diagram of chemical formula (I) for concerning between bismaleimide oligomer (combination of dimaleimide and barbituric acid) structure and lithium ion.
Following formula shows the relation between bismaleimide oligomer and the lithium ion.
The test of electrochemical stability degree
Selection standard battery stamen [Jelly Roll-numbering: 502030, be of a size of 5mm (height) * 20mm (wide) * 300mm (length)], electrolyte with Comparative Examples 1 and embodiment 1～embodiment 5 is poured in the standard cell stamen respectively lentamente, vacuumizes de-bubble and heat-sealing mouth.Each battery carries out the charge and discharge cycles test between 4.2 volts and 2.75 volts.Employed measurement equipment system is Arbin-modelBT2042 (USA), and the program that discharges and recharges, changes into and decides voltage (4.2 volts) charging after reaching 4.2 volts at first deciding electric current [150mA (0.5C)] charging, continue to electric current and subtract and reduce to till the 15Ma, this is charging once; Battery carries out deciding the discharge of electric current [150mA (0.5C)] subsequently, and capacitance exhausts in fully with battery, and this is once discharge.Finish once charging continuously and be called a charge and discharge cycles with the complete routine that once discharges.
Its result please refer to the 1st figure and the 2nd figure, the electrolyte that shows Comparative Examples 1 and embodiment 1～embodiment 5 discharges and recharges usefulness (R.T.cycle), has the electrolyte that contains the maleimide additive as we know from the figure and can make the follow-up electric capacitance change of battery present more stable situation.
The flame resistance test
Comparative Examples 1 is carried out flame resistance test with embodiment 4～6, and the result is as shown in table 2.As shown in Table 2, embodiment 4～6 contains the electrolyte of maleimide additive, and than tool thermal endurance and flame resistance, content has had suitable flame resistance at 1 weight percent, can be after burning things which may cause a fire disaster leave burn-out, and flame extinguishes rapidly.
Table 2: the flame resistance test result of Comparative Examples 1 and embodiment 4～6
| Comparative Examples 1 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Flame resistance | Burning stops flame and burnt away several minutes | Burning stops flame and stops at once | Burning stops flame and stops at once | Burning stops flame and stops at once |
In addition, the intersolubility of maleimide additive and electrolyte is good, it contains such as multiplicity functional groups (functional groups) such as the two keys of maleimide, carbonyl and imido grpups, can be when battery produces high temperature, absorb heat in order to carry out cross-linking polymerization, can enlist the services of suitable electrolyte, the effect of performance Thermalrun-away, just as in electrolyte, constructing the protection safety net one, the lifting of cell safety function there is its effect.
In sum; structure of functional groups such as the two keys of maleimide additive tool maleimide of the present invention, phenyl, carbonyl or imido grpup; can bring into play the machine-processed function of full gain of performance effect; comprise secondary cell electrolysis matter discharged and recharged usefulness, life-span circulation, electrochemical stability, thermal stability and flame resistance and the protection function that overcharges.In addition,, all can combine the suitableeest proportion of composing and structure is mated no matter as the additive of liquid state/half colloidal state/colloidal state/semisolid/solid electrolyte, the flexibility ratio height of utilization, and applicable territory is also wide.
Though the present invention discloses as above with preferred embodiment; yet the present invention is not limited to these embodiment; those skilled in the art; under the situation that does not break away from design of the present invention and scope; when can making various variations and modification to it, so protection scope of the present invention should be with being as the criterion that appended claims was defined.
Claims (20)
1. nonaqueous electrolytic solution that contains the maleimide additive that is used for alkali metal family secondary cell, this electrolyte comprises:
The electrolyte of alkali metal salt;
Nonaqueous solvents; And
Contain the maleimide additive, wherein this contains the maleimide additive and comprises maleimide, dimaleimide, bismaleimide oligomer or its combination.
2. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein the electrolyte of this alkali metal salt is selected from by 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)
4And LiCF
3SO
3The group of being formed.
3. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this nonaqueous solvents is selected from by ethylene carbonate, propylene carbonate, butylene carbonate, dipropyl carbonate, acid anhydrides, N-methyl pyrrolidone, the N-methylacetamide, the N-methylformamide, dimethyl formamide, diethylformamide, γ-butyl lactone, acetonitrile, methyl-sulfoxide and dimethyl sulfite, vinylene carbonate, carbonic acid first propyl ester, 1,3-dioxolanes, 1, the 2-diethoxyethane, 1, the 2-dimethoxy-ethane, 1,2-dibutoxy ethane, oxolane, the 2-methyltetrahydrofuran, expoxy propane, methyl acetate, ethyl acetate, methyl butyrate, ethyl butyrate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, the group that propyl acetate is formed.
4. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this adding proportion that contains the maleimide additive accounts for 0.01%～10% of electrolyte weight percentage.
5. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this adding proportion that contains the maleimide additive accounts for 0.1%～5% of electrolyte weight percentage.
6. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this maleimide has structure shown in formula (I) and the formula (II):
Formula (I) formula (II)
R wherein
1For-RCH
2-(alkyl) ,-RNH
2R ,-C (O) CH
3,-CH
2OCH
3,-CH
2S (O) CH
3,-C
6H
5,-CH
2(C
6H
5) CH
3, stretch phenyl, stretch xenyl, cyclic aliphatic, or the aromatic series of silane substituted; Y is-H-R ,-RCH
3,-C (CH
3)
3, or-S (O)-R ,-CONH
2,-C (CF
3)
3Deng; R
2Be H independently, F, Cl, Br, HSO
3, SO
2Or has an alkyl of 1-6 carbon; And R is the alkyl of 1-6 carbon.
7. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this maleimide is selected from by maleimide-phenyl for methane, phenyl maleimide, tolyl maleimide, 3,5-dimethylphenyl maleimide, vinyl maleimide, sulfo-maleimide, maleimide ketone, methylene maleimide, maleimide methyl ether, dimaleoyl imino-ethylene glycol, 4-phenylate-maleimide, group that the 4-maleimide-the benzene sulfone is formed.
8. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this dimaleimide has structure shown in formula (III) and the formula (IV):
Formula (III) formula (IV)
R wherein
3For-RCH
2-(alkyl) ,-RNH
2R-,-C (O) CH
2-,-CH
2OCH
2-,-C (O)-,-O-,-O-O-,-S-,-S-S-,-S (O)-,-CH
2S (O) CH
2-,-(O) S (O)-,-C
6H
5-,-CH
2(C
6H
5) CH
2-,-CH
2(C
6H
5) (O)-, stretch phenyl, stretch xenyl, the xenyl of stretching of stretching phenyl or replacement of replacement, and R
4For-RCH
2-,-C (O)-,-C (CH
3)
2-,-O-,-O-O-,-S-,-S-S-,-(O) S (O)-, or-S (O)-.
9. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this dimaleimide is selected from by N, N '-dimaleimide-4,4 '-diphenyl is for methane, 1,1 '-(di-2-ethylhexylphosphine oxide-4, the 1-phenylene) dimaleimide, N, N '-(1,1 '-diphenyl-4,4 '-dimethylene) dimaleimide, N, N '-(4-methyl isophthalic acid, the 3-phenylene) dimaleimide, 1,1 '-(3,3 '-dimethyl-1,1 '-diphenyl-4,4 '-dimethylene) dimaleimide, N, N '-vinyl dimaleimide, N, N '-(1, the 2-phenylene) dimaleimide, N, N '-(1, the 3-phenylene) dimaleimide, N, N '-dimaleimide sulphur, N, N '-dimaleimide two sulphur, N, N '-dimaleimide ketone, N, N '-methylene dimaleimide, dimaleimide first-ether, 1,2-dimaleimide base-1,2-ethylene glycol, N, N '-4,4 '-diphenyl ether-dimaleimide, 4,4 '-group that dimaleimide-diphenyl sulphone (DPS) is formed.
10. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, wherein this bismaleimide oligomer is obtained by dimaleimide monomer and barbituric acid reaction.
11. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 10, wherein this bismaleimide oligomer is the polyfunctional group bismaleimide oligomer of high branched structure of a kind of tool or many pairs of key reactive functional groups.
12. the nonaqueous electrolytic solution that contains the maleimide additive according to claim 11, wherein this high branched structure mainly is to be structural matrix with the dimaleimide, on two keys of this barbituric acid with its free radical form grafting dimaleimide, make two keys of dimaleimide can open bilateral or one-sided, and the configuration organized polymerization that carries out collateralization and prefaceization reacts, prop up a segmented structure in order to form, and lasting graft polymerization becomes high branched structure.
13. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 11, wherein this its segment of high branched structure is combined as-[(dimaleimide monomer)+(barbituric acid)
x]
m-, X is 0～4, and number of repeat unit m value is less than 20.
14. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 11, wherein X is 0.5～2.5,, and number of repeat unit m value is between 2～10.
15. the nonaqueous electrolytic solution that contains the maleimide additive according to claim 11, wherein this high branched structure is the branch kenel, each branch is a segment, and general branch's segment of this high branched structure is-and { [(dimaleimide monomer)+(barbituric acid)
x]
m}
n-, wherein X is 0～4, number of repeat unit m value is less than 20, and the repetitive n value of general branch's segment is less than 50.
16. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 10, wherein this barbituric acid has structure shown in the formula (V):
Wherein, R
5And R
6Substituting group for identical or different comprises H, CH
3, C
2H
5, C
6H
5, CH (CH
3)
2, CH
2CH (CH
3)
2, CH
2CH
2CH (CH
3)
2, or
17. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 10, wherein the reaction mol ratio of the dimaleimide of synthetic this bismaleimide oligomer and barbituric acid is 100: 1～1: 1.
18. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 10, wherein the reaction mol ratio of the dimaleimide of synthetic this bismaleimide oligomer and barbituric acid is 20: 1～1: 1.
19. according to the nonaqueous electrolytic solution that contains the maleimide additive of claim 1, also comprises surfactant, viscosity reductant or carbonate.
20. an alkali metal family secondary cell comprises:
Positive pole and negative pole;
Barrier film is located between this positive pole and this negative pole; And
The nonaqueous electrolytic solution that contains the maleimide additive according to claim 1.
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