CN100424926C - High ion conductivity colloid polyelectrolyte for chargeable and dischargeable polymer secondary battery - Google Patents
High ion conductivity colloid polyelectrolyte for chargeable and dischargeable polymer secondary battery Download PDFInfo
- Publication number
- CN100424926C CN100424926C CNB2005101158704A CN200510115870A CN100424926C CN 100424926 C CN100424926 C CN 100424926C CN B2005101158704 A CNB2005101158704 A CN B2005101158704A CN 200510115870 A CN200510115870 A CN 200510115870A CN 100424926 C CN100424926 C CN 100424926C
- Authority
- CN
- China
- Prior art keywords
- bismaleimides
- methyl
- colloidal condition
- carbonate
- precursor compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the colloidal polyelectrolyte and its predecessor for secondary cell. Wherein, the predecessor is made of barbituric acid and bismaleimide, and can be injected into the Al-foil bag on cell outside shell to penetrate the isolation film and generate polyelectrolyte after in-situ heating polymerization.
Description
Technical field
The invention relates to a kind of colloidal condition macromolecule electrolyte of secondary cell, and precursor composition, especially this precursor composition can be irritated in the liquid process injection battery case aluminium foil bag by liquid, via real-time heat hot polymerization (in-situ heating polymerization), and penetrate barrier film polymerization generation colloidal condition macromolecule electrolyte.
Background technology
Along with the fast-developing and generalization of portable electronic product, lithium rechargeable battery makes its demand and day hurriedly increase because of in light weight and characteristics such as tool high voltage and high-energy-density.In addition, when the demand of electronic product during, use polyelectrolyte in lithium rechargeable battery thereby press for, and cause broad research towards thin littleization and the development of tool flexibility.
The lithium ion macromolecule battery uses polyelectrolyte that many advantages are arranged, the danger of no electrolyte leakage, can make ultra-thin large tracts of land or angled battery, in light weight, lower vapour pressure and self-discharge rate, increase lithium rechargeable battery widely in the coml effect.
For the thin battery (thin type battery) of studying tool pliability sheet type shell, existing several colloidal condition macromolecule material fit electrolyte compositions are studied, such as poly(ethylene oxide) (PEO), polymethyl methacrylate (PMMA), Kynoar (PVDF), polyacrylonitrile system and derivative condensate or copolymer such as (PAN).The electrolytical processing procedure of colloidal condition macromolecule that general macromolecule battery is used, be to desolvate after its film forming earlier, again polymeric membrane is positioned over active material interlayer storehouse or coats the active material surface and make battery, then pour into liquid electrolyte, and will stick together between the battery lead plate, therefore the embedding and the embedding of lithium ion goes out in charge and discharge process, reduces the expansion or the contraction of pole plate sandwich construction, battery long service life, but processing procedure complexity.
Summary of the invention
Colloidal condition macromolecule electrolyte of the present invention does not have the problem of electrolyte leakage, so battery has reliability (reliability) preferably; This colloidal condition macromolecule material and electrolyte intersolubility are good in addition; The bridge formation structure that produces remains in inside with solvent, and electrolyte retentivity (retainability) is good and very high to lithium salts solubility, and very high ionic conductivity is arranged; Macromolecule predecessor prescription of the present invention, irritating the liquid process according to general liquid injects in the battery case aluminium foil bag, via real-time heat hot polymerization (in-situ heating polymerization), and penetrate the barrier film polymerization and produce the colloidal condition macromolecule electrolyte, wherein two kinds of macromolecule predecessors form copolymerzation with cross-linking body (eopolymers), the simple and easy facility of processing procedure.
The polyelectrolyte of lithium macromolecule secondary cell of the present invention is formed (one) used for electrolyte macromolecule predecessor, form and (1) a kind of elder generation is arranged through a kind of polymerisable monomer of modified bismaleimide oligomer (modified-bismaleimideoligomer) (2) (monomers) or oligomer (oligomers), comprise alkyl methacrylate (alkyl methacrylate groups), propylene ester (acrylate groups), methacrylates (methacrylate groups) etc. are with chemical formula CH
2=C (CH
3) C (O) O-(C
yH
2yO)
mR
1' expression, y=0～3 wherein, m=1～9 above-mentionedly comprise one or more; Or comprising alkyl propylene cyanogen (alkyl acrylnitrilegroups), propylene cyanogen (acrylnitrile groups) etc. are with chemical formula R
2'-CH=C (CN) expression is formed the copolymer that is produced for these two kinds.(2) contain two kinds of mixed solvents at least, first kind of solvent has high boundary's electric constant and high viscosity.Second kind of solvent has characteristics such as lower boundary's electric constant and low-viscosity.Ethylene carbonate (Ethylene Carbonate, EC) and propylene carbonate (Propylene Carbonate, EC) and gamma-butyrolacton (γ-butyrolactone GBL) waits it to have high dielectric constant.(3) the lithium salt LiPF that dissociates
6, LiBF
4Deng.(4) free radical starting agent.(5) additive, common additive have vinylene carbonate (Vinylene Carbonate), sulphite (sulfites), sulfate (sulfates), phosphonate ester or derivatives thereof compound.
Above-mentioned polyelectrolyte predecessor prescription, irritating the liquid process according to general liquid electrolyte injects in the battery case aluminium foil bag, battery is behind canned program, produce thermal polymerization (in-situ heatingpolymerization) through heating in real time again, molecule penetrates the barrier film polymerization and produces the colloidal condition macromolecule electrolyte in heat polymerization carries out, 30～130 ℃ of thermal polymerization temperature ranges, wherein two kinds of macromolecule predecessors form cross-linking type co-polymer (copolymers), the colloidal condition macromolecule electrolyte can cohere the both positive and negative polarity pole plate, and processing procedure is simple and easy.
Preferable concrete enforcement state of the present invention includes, but is not limited to following items:
1. colloidal condition macromolecule electrolyte precursor compositions that can be used for secondary cell comprises:
A) the bismaleimides oligomer of modification is generated by barbiturates (barbituric acid) and bismaleimides (bismaleimide) reaction;
B) one or more are with CH
2=C (R
0) C (O) O-(C
yH
2yO)
mR
1Acrylic acid (ester) the class monomer of expression, y=1～3 wherein, m=0～9, R
0Be hydrogen or methyl, R
1Be hydrogen, hydroxyl, C1～C6 alkyl, C1～C6 alkoxyl, C2～C6 thiazolinyl, C3～C6 cycloalkyl or phenyl; One or more are with R
2-CH=C (R
0) (CN) the alkene nitrile monomer of expression, R wherein
0Definition the same, R
2Be hydrogen, hydroxyl, C1～C6 alkyl, C1～C6 alkoxyl, C2～C6 thiazolinyl, C3～C6 cycloalkyl or phenyl; Or their oligomer;
C) non-aqueous slaine electrolyte;
D) aprotic solvent; And
E) free radical starting agent,
Wherein with a) to d) weight and be benchmark, a) account for 1～50%; B) account for 1～50%; C) at d) concentration be 0.5M to 2M; And d) accounts for 10～90%; And e) be composition b) weight 0.1～5%.
2. as to begin a project the 1st colloidal condition macromolecule electrolyte precursor compositions, wherein composition is a) by one or more preparations of following barbiturates:
Wherein R ' and R " distinctly be-H ,-CH
3,-C
2H
5,-C
6H
5,-CH (CH
3)
2,-CH
2CH (CH
3)
2,-CH
2CH
2CH (CH
3)
2Or-C (CH
3) HCH (CH
3)
2
3. as to begin a project the 2nd colloidal condition macromolecule electrolyte precursor compositions, wherein R ' and R " be simultaneously-H.
4. as to begin a project the 1st, 2 or 3 colloidal condition macromolecule electrolyte precursor compositions, wherein composition is a) by one or more preparations of following bismaleimides:
R wherein
3Be C1～4 alkylene (alkylene) ,-CH
2NHCH
2-,-C
2H
4NHC
2H
4-,-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)-,-CH
2(C
6H
4) CH
2-,-CH
2(C
6H
4) O-, phenylene (phylene), biphenylene, the phenylene of replacement or the biphenylene of replacement; And R
4Be C1～4 alkylene ,-C (O)-,-C (CH
3)
2-,-O-,-O-O-,-S-,-S-S-,-(O) S (O)-, or-S (O)-.
5. as to begin a project the 4th colloidal condition macromolecule electrolyte precursor compositions, bismaleimides wherein is selected from N, N '-bismaleimides-4,4 '-diphenyl methane (N, N '-bismaleimide-4,4 '-diphenylmethane), 1,1 '-(di-2-ethylhexylphosphine oxide-4, the 1-phenylene) bismaleimides [1,1 '-(methylenedi-4,1-phenylene) bismaleimide], N, N '-(1,1 '-diphenyl-4,4 '-dimethylene) bismaleimides [N, N '-(1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, N '-(4-methyl isophthalic acid, the 3-phenylene) bismaleimides [N, N '-(4-methyl-1,3-phenylene) bismaleimide], 1,1 '-(3,3 '-dimethyl-1,1 '-diphenyl-4,4 '-dimethylene) bismaleimides [1,1 '-(3,3 ' dimethyl-1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, 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], 1,1 '-hexyl, two subunits-two pyrroles-2,5-diketone (1,1 '-hexanediyl-bis-pyrrole-2,5-dione), N, N '-two-(2, the two carbonyls-2 of 5-, the two hydrogen base-pyrroles of 5--1-carboxyl methylene amide [N, N '-bis-(2,5-dioxo-2,5-dihydro-pyrrole-1-carboxyl)-methylenediamine], 1,1 '-(3,3 '-piperazine-1,4-two subunits-dipropyl) two pyrroles-2, the 5-diketone [1,1 '-(3,3 '-piperazine-1,4-diyl-dipropyl) bis-pyrrole-2,5-dione], N, and N '-bismaleimides sulphur (N, N '-thiodimaleimid), N, N '-bismaleimides two sulphur (N, N '-dithiodimaleimid), N, and N '-bismaleimides ketone (N, N '-ketonedimaleimid), N, N '-di-2-ethylhexylphosphine oxide maleimide (N, N '-methylene-bis-maleinimid), bismaleimides first-ether (bis-maleinimidomethyl-ether), 1,2-dimaleoyl imino-1,2-ethylene glycol [1,2-bis-(maleimido)-1,2-ethandiol], N, N '-4,4 '-diphenyl ether-bismaleimides (N, N '-4,4 '-diphenylether-bis-maleimid), 4, the group of 4 '-bismaleimides-diphenyl sulphone (DPS) [4,4 '-bis (maleimido)-diphenylsulfone].
6. as to begin a project the 1st, 2 or 3 colloidal condition macromolecule electrolyte precursor compositions, wherein composition a) the bismaleimides oligomer generate in the reaction of 100～150 ℃ and 0.5～8 hour by barbiturates and bismaleimides.
7. as to begin a project the 1st colloidal condition macromolecule electrolyte precursor compositions, composition b wherein) comprise a kind of with CH
2=C (R
0) C (O) O-(C
yH
2yO)
mR
1Acrylic acid (ester) the class monomer of expression, y=1～3 wherein, m=1～9, R
0Be methyl, and R
1Be hydrogen.
8. as to begin a project the 7th colloidal condition macromolecule electrolyte precursor compositions, composition b wherein) further comprise methyl methacrylate monomer.
9. as to begin a project the 1st colloidal condition macromolecule electrolyte precursor compositions, composition b wherein) comprise methyl methacrylate monomer.
10. as to begin a project the 1st colloidal condition macromolecule electrolyte precursor compositions, composition c wherein) be selected from 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
3And composition thereof the group that formed.
11. as to begin a project the 1st colloidal condition macromolecule electrolyte precursor compositions, ingredient d wherein) aprotic solvent is to comprise a mixed solvent that is selected from following two kinds of solvents, first kind of solvent has high dielectric constant and high viscosity, second kind of solvent has lower dielectric constant and low-viscosity, this first kind of solvent is selected from ethylene carbonate (ethylene carbonate, EC), propene carbonate (propylene carbonate, PC), butylene (butylene carbonate), carbonic acid dipropyl (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), gamma-butyrolacton (γ-butyrolactone), acetonitrile (acetonitrile), the group that methyl-sulfoxide (dimethyl sulfoxide) and dimethyl sulfite (dimethyl sulfite) are formed; This second kind of solvent is ethers, ester class or carbonic ester, and this ethers is to be selected from 1,2-diethoxyethane (1,2-diethoxyethane), 1,2 dimethoxy-ethane (1,2-dimethoxyethane), 1,2 dibutoxy ethane (1,2-dibutoxyethane), oxolane (tetrahydrofuran), 2-methyltetrahydrofuran (2-methyltetrahydrofuran), the group that expoxy propane (propylene oxide) is formed; This ester class is selected from methyl acetate (methyl acetate), ethyl acetate (ethyl acetate), methyl butyrate (methyl butyrate), ethyl butyrate (ethyl butyrate), methyl propionate (methyl proionate), the group that ethyl propionate (ethyl proionate) is formed; And this carbonic ester is selected from dimethyl carbonate, and (Dimethyl Carbonate, DMC), (Diethyl Carbonate is DEC) with carbonic acid Methylethyl ester (Ethyl Methyl Carbonate, the EMC) group that is formed for diethyl carbonate.
12. as to begin a project the 11st colloidal condition macromolecule electrolyte precursor compositions, ingredient d wherein) aprotic solvent comprises ethylene carbonate (ethylene carbonate, EC), propene carbonate (propylene carbonate, PC), and diethyl carbonate (Diethyl Carbonate, DEC).
13. as to begin a project the 12nd colloidal condition macromolecule electrolyte precursor compositions, ingredient d wherein) aprotic solvent, by volume, the scope of ethylene carbonate is 10% to 50%, the scope of propene carbonate is 5% to 80%, and the scope of diethyl carbonate is 3% to 75%.
14. as to begin a project the 1st colloidal condition macromolecule electrolyte precursor compositions, ingredient e wherein) free radical starting agent is selected from peroxidating ketone (ketone peroxide), ketal peroxide class (peroxy ketal), hydroperoxide kind (hydroperoxide), the two alkanes (dialkyl peroxide) of peroxidating, peroxidating non-annularity alkanes (diacyl peroxide), peroxyesters (peroxy ester) reaches the group that azo-compound (azo compound) is formed.
15. as to begin a project the 1st colloidal condition macromolecule electrolyte precursor compositions, ingredient e wherein) free radical starting agent is the two isobutyl group eyeballs (2 of azo, 2-azo-bis-isobutyronitrile, AIBN), phenylazo triphenylmenthane (phenyl-azo-triphenylmethane), peroxidating the 3rd butane (t-butyl peroxide, TBP), peroxidating cumene (cumyl peroxide), acetyl peroxide (acetyl peroxide), dibenzoyl peroxide (benzoyl peroxide, BPO), dilauroyl peroxide (lauroyl peroxide), tributyl hydrogen peroxide (t-butyl hydroperoxide), or tributyl perbenzoate (t-butyl perbenzoate).
16. a macromolecule lithium secondary battery, it comprises:
I) negative pole, but its electrochemistry embeds/moves out alkali metal;
Ii) a positive pole comprises electrochemistry and embeds/move out alkali-metal electrode active material; And
Iii) a kind of negative pole and anodal colloidal condition macromolecule electrolyte of activating, wherein this colloidal condition macromolecule electrolyte is to prepare via heated polymerizable/crosslinked as to begin a project each described colloidal condition macromolecule electrolyte precursor compositions in the 1st to 15.
17. as to begin a project the 16th macromolecule lithium secondary battery, wherein this negative pole comprises a negative pole activating substance, and it is to be selected to comprise: the group that surely mutually spherical carbon (MCMB), vapor deposition carbon fiber (VGCF), CNT (carbon nano-tube) (CNT), coke, carbon black, graphite, acetylene black, carbon fiber and nature of glass carbon and its mixture are formed.
18. as to begin a project the 16th macromolecule lithium secondary battery, wherein this negative pole further comprises the fluororesin binder.
19. as to begin a project the 16th macromolecule lithium secondary battery, electrode active material that wherein should positive pole is the lithiumation oxide that is selected from vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt and manganese, lithiumation sulfide, lithiumation selenides, and the group that forms of lithiumation tellurides and its mixture.
20. as, wherein should further comprise the fluororesin binder by positive pole to begin a project the 17th macromolecule lithium secondary battery.
21. as, wherein should positive pole further comprise and be selected from acetylene black, carbon black, graphite, nickel powder, aluminium powder, titanium valve and stainless steel powder and its mixture is formed one of group conductive additive to begin a project the 17th macromolecule lithium secondary battery.
The present invention can further be understood by following examples, and these embodiment but not are used to limit the scope of the invention as illustrative purposes only.
Description of drawings
Fig. 1 shows the present invention that the embodiment of the invention 6 is prepared and the charge and discharge cycles of known colloidal condition macromolecule lithium secondary battery.
Fig. 2 shows the present invention that the embodiment of the invention 7 is prepared and the charge and discharge cycles of known colloidal condition macromolecule lithium secondary battery.
Fig. 3 shows the charge and discharge cycles of the embodiment of the invention 8 prepared colloidal condition macromolecule lithium secondary battery of the present invention under different gelatinization temperatures.
Embodiment
Embodiment 1: the preparation of the bismaleimides oligomer of modification
Bismaleimides (bismaleimide) is mixed with mol ratio 3/1～10/1 with barbiturates (barbituric acid), add solvent gamma-butyrolacton (γ-butyrolactone, GBL) or propene carbonate (propylenecarbonates) etc., heating answers temperature at 100～150 ℃, in 0.5～8 hour reaction time, reaction generates bismaleimides oligomer (bismaleimide oligomer).Use the listed partition of table one to reach the bismaleimides oligomer that prepare modifications at 130 ℃ in this example.
Table one
| Weight | |
| N, N '-bismaleimides-4,4 '-diphenyl is for methane (N, N '-bismaleimide-4,4 '-diphenylmethane) | 59.613g |
| Barbiturates | 2.132g |
| Gamma-butyrolacton | 247.059g |
Embodiment 2: the preparation of colloidal condition macromolecule
The prescription of present embodiment use table two prepares colloidal condition macromolecule, have comprising use embodiment 1 modification the bismaleimides oligomer example of the present invention and do not contain the reference examples of bismaleimides oligomer of modification.List file names with whether the colloidal condition macromolecule prescription produces gel under 25 ℃ and 80 ℃ gel time in the table two.
Table two
*This prescription contains in the two isobutyl group nitriles of the azo of the total weight 1% of monomer and oligomer
(2,2-azo-bis-isobutyronitrile, AIBN) free radical starting agent
AN: acrylonitrile (acrylnitrile)
MMA: methyl methacrylate (methyl methacrylate)
The bismaleimides oligomer of the modification of M-BMI: embodiment 1
PEGMA: methacrylic acid macrogol ester (poly (ethylene glycol) methacrylate)
PEGDA: polyethyleneglycol diacrylate (poly (ethylene glycol) diacrylate)
O.5～1 hour the bismaleimides oligomer of the modification of embodiment 1 can polymerization formation colloidal condition macromolecule under heating and in the presence of the AIBN free radical starting agent and in the short time as can be seen from the result of table two, and reaction rate is fast.
Embodiment 3: electrolytical preparation of colloidal condition macromolecule and ionic conductivity
Use multiple different prescription to prepare colloidal condition macromolecule electrolyte precursor thing in the present embodiment, carry out gel in 80 ℃ again.With ac resistance analysis (AC impendance) measure the impedance of ions diffusion section, bring the ionic conductivity formula again into and try to achieve ionic conductivity σ=L/A * R and try to achieve ionic conductance, wherein L is a thickness, A is that area and R are resistance.
One general preparation process is that lithium slaine electrolyte is mixed with aprotic solvent, obtains an electrolyte solution; Preparation monomer/oligomer/free radical plays the mixture of agent; Mix this electrolyte solution and this mixture, obtain colloidal condition macromolecule electrolyte precursor thing; Jia Re formation colloidal condition macromolecule electrolyte again.
Following table three is listed conventional liquid electrolyte and the electrolytical prescription of colloidal condition macromolecule of the present invention, and ionic conductance.
Table three
*Electrolyte solution is by LiPF
6Concentration is that the EC/GBL=1/3 of 1M forms; The macromolecule predecessor is formed (including AIBN 1%) by the bismaleimides oligomer of the modification that contains the MMA and the embodiment of the invention 1
Experimental result by above-mentioned table three is learnt, when the content of macromolecule predecessor in the prescription is that bismaleimides oligomer (M-BMI) content of 10 weight % and modification of the present invention is when being 5 weight %, after 80 ℃ of heating, can be grouped to the colloidal condition macromolecule electrolyte, though and its ionic conductivity is kept very high ionic conductivity 9.3mS/cm less than the 10.1mS/cm of liquid electrolyte.
Embodiment 4: electrolytical preparation of colloidal condition macromolecule and ionic conductivity
The step that repeats embodiment 3 prepares the colloidal condition macromolecule electrolyte, use respectively in the macromolecule predecessor wherein embodiment 1 modification bismaleimides oligomer (M-BMI) and compare polyethyleneglycol diacrylate (PEGDA) monomer of usefulness, show that the former colloidal condition macromolecule electrolyte of the present invention has the ionic conductivity of obvious improvement.Table four is listed the composition and the result of prescription.
Table four
*The electrolyte solution of experiment 4 and 5 is by LiPF
6Concentration is that the EC/GBL=1/3 of 1M forms; The electrolyte solution of experiment 6 and 7 is by LiPF
6Concentration is that the EC/PC=1/1 of 1M forms
Macromolecule predecessor/electrolyte solution the prescription of above-mentioned experiment 4～7 forms the colloidal condition macromolecule electrolyte through heated polymerizable, and wherein testing 4 and 5 electrolyte solution is 1M LiPF
6EC/GBL=1/3, the macromolecule predecessor that relatively adds M-BMI and PEGDA is formed, visible ionic conductivity raising 25% clearly; And at the electrolyte solution 1M LiPF that tests 6 and 7
6The EC/PC=1/1 system, four times of the macromolecule predecessor ratio of components adding PEGDA person's of adding M-BMI ionic conductivity raisings clearly.
Embodiment 5: electrolytical preparation of colloidal condition macromolecule and ionic conductivity
The step that repeats embodiment 3 prepares the colloidal condition macromolecule electrolyte, uses the modified bismaleimide oligomer (M-BMI) of embodiment 1 in the macromolecule predecessor wherein respectively and compares the different monomers of usefulness.Table five is listed the composition and the result of prescription.
Table five
*The electrolyte solution of experiment 8～11 is by LiPF
6Concentration is that the EC/GBL=1/3 of 1M forms;
TEGEEA:Tri (ethylene glycol) ethyl ether acrylate, ethyl triethylene glycol ether acrylate;
PEGDMA:polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate.
Macromolecule predecessor/electrolyte solution the prescription of above-mentioned experiment 8～11 forms the colloidal condition macromolecule electrolyte through heated polymerizable, wherein tests 8 the present invention that add by M-BMI and forms the significantly higher 4.75mS/cm of being of its ionic conductivity.
The preparation of colloidal condition macromolecule lithium secondary battery and capacitance characteristic
The preparation of colloidal condition macromolecule lithium secondary battery comprises part: the manufacturing of positive and negative pole plate, barrier film, colloidal condition macromolecule electrolyte; The colloidal condition macromolecule electrolyte comprises macromolecule predecessor and liquid electrolyte solution.
Positive and negative electrode pole plate production method is identical with known lithium rechargeable battery, is all through coating method and carries out, and anode sizing agent is 80～95% LiCoO
2, acetylene black 3～15% is dissolved in NMP (N-N-methyl-2-2-pyrrolidone N-) solvent with binder PVDF 3～10% and forms, slurry is uniformly coated on long 300 meters as the formed ink, wide 35 centimeters, the aluminum foil coil of thick 20 μ m, dried anodal volume need roll and itemize, at last again with 110 ℃ of vacuumizes 4 hours.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 binder is polyvinylidene fluoride (PVDF) for example; The conductivity activator can be carbon black, graphite, acetylene black, nickel powder, aluminium powder, titanium valve and stainless steel powder or the like.
Cathode size then is dissolved in 10% the solution that PVDF and NMP formed for the toner body 90% of diameter 1 μ m～30 μ m, after waiting to stir, be coated on long 300 meters, wide 35 centimeters, the Copper Foil volume of thick 10 μ m, formed negative pole volume through roll and itemize after, equally again with 110 ℃ of vacuumizes 4 hours.Negative electrode active material can be situated between surely mutually spherical carbon (MCMB), vapor deposition carbon fiber (VGCF), CNT (carbon nano-tube) (CNT), coke, carbon black, graphite, acetylene black, carbon fiber and nature of glass carbon; The fluororesin binder is polyvinylidene fluoride (PVDF) for example.Be provided at dry environment such as glove box or hothouse through the made positive and negative electrode of vacuumize.
Embodiment 6:
Get 6 batteries and be divided into two groups of experiments, experiment A macromolecule predecessor consists of: MEMA: M-BMI=7: 1, and electrolyte solution is LiPF
6The EC/DEC/PC=3/5/2 of concentration 1M; And macromolecule predecessor: electrolyte solution=20: 80, M-BMI:3%, wherein MEMA represents methoxy tri (ethyleneglycol) methacrylate, methyl triethylene glycol ether metacrylic acid ester.Experiment B macromolecule predecessor consists of: MEMA: PEGDA258=7: 1, and electrolyte solution is LiPF
6The EC/DEC/PC=3/5/2 of concentration 1M; And macromolecule predecessor: electrolyte solution=20: 80, PEGDA258:3%.Aluminium foil bag macromolecule battery model 383562, battery assembling are finished through 3 hours macromolecule predecessors of 85 ℃ of heating in the inside battery polymerization, and battery charging and discharging speed is adopted 0.2C charging and discharge.Shown in the charge and discharge cycles of Fig. 1, the battery of experiment A: initial capacitance 760mAh, discharging and recharging afterwards through 50 times, capacitance maintains 710mAh; The battery of experiment B: initial capacitance 710mAh, discharging and recharging afterwards through 50 times, capacitance maintains 410mAh.Experimental result learns that prescription contains M-BMI reasonable capacitance and battery life are arranged.
Embodiment 7:
Get 6 batteries and be divided into two groups of experiments, experiment C macromolecule predecessor consists of: MEMA: M-BMI=7: 1, and electrolyte solution is LiPF
6The EC/GBL=1/3 of concentration 1M; And macromolecule predecessor: electrolyte solution=20: 80, M-BMI:3%.Experiment D macromolecule predecessor consists of: MEMA: PEGDA258=7: 1, and electrolyte solution is LiPF
6The EC/GBL=1/3 of concentration 1M; And macromolecule predecessor: electrolyte solution=20: 80, PEGDA258:3%.Aluminium foil bag macromolecule battery model 383562, battery assembling are finished through 3 hours macromolecule predecessors of 85 ℃ of heating in the inside battery polymerization, and battery charging and discharging speed is adopted 0.2C charging and discharge.Shown in the charge and discharge cycles of Fig. 2, the battery of experiment C: initial capacitance 650mAh, discharging and recharging afterwards through 60 times, capacitance maintains 560mAh; The battery of experiment D: initial capacitance 730mAh, discharging and recharging afterwards through 60 times, capacitance maintains 430mAh.Experimental result learns that prescription contains M-BMI reasonable capacitance and battery life are arranged.
Embodiment 8:
Get 15 batteries and be divided into five groups of experiments, every group of macromolecule predecessor consists of: MEMA: M-BMI=7: 1, and electrolyte solution is LiPF
6The EC/DEC/PC=3/5/2 of concentration 1M; And macromolecule predecessor: electrolyte solution=20: 80, M-BMI:3%.Aluminium foil bag macromolecule battery model 383562, through different temperatures heating 3 hours, the macromolecule predecessor was in the inside battery polymerization, and battery charging and discharging speed is adopted 0.2C charging and discharge.Experiment E, F, G, H and I heating-up temperature are respectively 75 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃.Fig. 3 demonstration discharges and recharges the result: experiment G, and 90 ℃ have preferable battery life, initial capacitance 660mAh, discharging and recharging afterwards through 20 times, capacitance maintains 636mAh.
Claims (21)
1. colloidal condition macromolecule electrolyte precursor compositions that can be used for secondary cell comprises:
A) the bismaleimides oligomer of modification is generated by barbiturates (barbituric acid) and bismaleimides (bismaleimide) reaction;
B) one or more are with CH
2=C (R
0) C (O) O-(C
yH
2yO)
mR
1The acrylic acid or the acrylic ester monomer of expression, y=1～3 wherein, m=0～9, R
0Be hydrogen or methyl, R
1Be hydrogen, hydroxyl, C1～C6 alkyl, C1～C6 alkoxyl, C2～C6 thiazolinyl, C3～C6 cycloalkyl or phenyl; One or more are with R
2-CH=C (R
0) (CN) the alkene nitrile monomer of expression, R wherein
0Definition the same, R
2Be hydrogen, hydroxyl, C1～C6 alkyl, C1～C6 alkoxyl, C2～C6 thiazolinyl, C3～C6 cycloalkyl or phenyl; Or their oligomer;
C) non-aqueous slaine electrolyte;
D) aprotic solvent; And
E) free radical starting agent,
Wherein with a) to d) weight and be benchmark, a) account for 1～50%; B) account for 1～50%; C) at d) concentration be 0.5M to 2M; And d) accounts for 10～90%; And e) be composition b) weight 0.1～5%.
2. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 1, wherein composition is a) by one or more preparations of following barbiturates:
Wherein R ' and R " distinctly be-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-C (CH
3) HCH (CH
3)
2
3. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 2, wherein R ' and R " be simultaneously-H.
4. as claim 1,2 or 3 described colloidal condition macromolecule electrolyte precursor compositions, wherein composition is a) by one or more preparations of following bismaleimides:
R wherein
3Be C 1～4 alkylene ,-CH
2NHCH
2-,-C
2H
4NHC
2H
4-,-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)-,-CH
2(C
6H
4) CH
2-,-CH
2(C
6H
4) O-, phenylene, biphenylene, the phenylene of replacement or the biphenylene of replacement; And R
4Be C1～4 alkylene ,-C (O)-,-C (CH
3)
2-,-O-,-O-O-,-S-,-S-S-,-(O) S (O)-, or-S (O)-.
5. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 4, bismaleimides wherein is selected from N, N '-bismaleimides-4,4 '-diphenyl methane (N, N '-bismaleimide-4,4 '-diphenylmethane), 1,1 '-(di-2-ethylhexylphosphine oxide-4, the 1-phenylene) bismaleimides [1,1 '-(methylenedi-4,1-phenylene) bismaleimide], N, N '-(1,1 '-diphenyl-4,4 '-dimethylene) bismaleimides [N, N '-(1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, N '-(4-methyl isophthalic acid, the 3-phenylene) bismaleimides [N, N '-(4-methyl-1,3-phenylene) bismaleimide], 1,1 '-(3,3 '-dimethyl-1,1 '-diphenyl-4,4 '-dimethylene) bismaleimides [1,1 '-(3,3 ' dimethyl-1,1 '-biphenyl-4,4 '-diyl) bismaleimide], N, 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], 1,1 '-hexyl, two subunits-two pyrroles-2,5-diketone (1,1 '-hexanediyl-bis-pyrrole-2,5-dione), N, N '-two-(2, the two carbonyls-2 of 5-, the two hydrogen base-pyrroles of 5--1-carboxyl methylene amide [N, N '-bis-(2,5-dioxo-2,5-dihydro-pyrrole-1-carboxyl)-methylenediamine], 1,1 '-(3,3 '-piperazine-1,4-two subunits-dipropyl) two pyrroles-2, the 5-diketone [1,1 '-(3,3 '-piperazine-1,4-diyl-dipropyl) bis-pyrrole-2,5-dione], N, and N '-bismaleimides sulphur (N, N '-thiodimaleimid), N, N '-bismaleimides two sulphur (N, N '-dithiodimaleimid), N, and N '-bismaleimides ketone (N, N '-ketonedimaleimid), N, N '-di-2-ethylhexylphosphine oxide maleimide (N, N '-methylene-bis-maleinimid), bismaleimides first-ether (bis-maleinimidomethyl-ether), 1,2-dimaleoyl imino-1,2-ethylene glycol [1,2-bis-(maleimido)-1,2-ethandiol], N, N '-4,4 '-diphenyl ether-bismaleimides (N, N '-4,4 '-diphenylether-bis-maleimid), 4, the group of 4 '-bismaleimides-diphenyl sulphone (DPS) [4,4 '-bis (maleimido)-diphenylsulfone].
6. as claim 1,2 or 3 described colloidal condition macromolecule electrolyte precursor compositions, wherein composition a) the bismaleimides oligomer by barbiturates and bismaleimides in the reaction of 100～150 ℃ and 0.5～8 hour and generate.
7. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 1, composition b wherein) comprise a kind of with CH
2=C (R
0) C (O) O-(C
yH
2yO)
mR
1The acrylic ester monomer of expression, y=1～3 wherein, m=1～9, R
0Be methyl, and R
1Be hydrogen.
8. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 7, composition b wherein) further comprise methyl methacrylate monomer.
9. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 1, composition b wherein) comprise methyl methacrylate monomer.
10. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 1, composition c wherein) be selected from 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
3And composition thereof the group that formed.
11. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 1, ingredient d wherein) aprotic solvent is to comprise a mixed solvent that is selected from following two kinds of solvents, first kind of solvent has high dielectric constant and high viscosity, second kind of solvent has lower dielectric constant and low-viscosity, this first kind of solvent is selected from ethylene carbonate (ethylene carbonate, EC), propylene carbonate (propylene carbonate, PC), butylene (butylene carbonate), carbonic acid dipropyl (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), gamma-butyrolacton (γ-butyrolactone), acetonitrile (acetonitrile), the group that methyl-sulfoxide (dimethyl sulfoxide) and dimethyl sulfite (dimethyl sulfite) are formed; This second kind of solvent is ethers, ester class or carbonic ester, and this ethers is to be selected from 1,2-diethoxyethane (1,2-diethoxyethane), 1,2 dimethoxy-ethane (1,2-dimethoxyethane), 1,2 dibutoxy ethane (1,2-dibutoxyethane), oxolane (tetrahydrofuran), 2-methyltetrahydrofuran (2-methyltetrahydrofuran), the group that expoxy propane (propylene oxide) is formed; This ester class is selected from methyl acetate (methyl acetate), ethyl acetate (ethyl acetate), methyl butyrate (methyl butyrate), ethyl butyrate (ethyl butyrate), methyl propionate (methyl proionate), the group that ethyl propionate (ethyl proionate) is formed; And this carbonic ester is selected from dimethyl carbonate, and (Dimethyl Carbonate, DMC), (Diethyl Carbonate is DEC) with carbonic acid Methylethyl ester (Ethyl Methyl Carbonate, the EMC) group that is formed for diethyl carbonate.
12. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 11, ingredient d wherein) aprotic solvent comprises ethylene carbonate (ethylene carbonate, EC), propene carbonate (propylenecarbonate, PC), and diethyl carbonate (Diethyl Carbonate, DEC).
13. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 12, ingredient d wherein) aprotic solvent, by volume, the scope of ethylene carbonate is 10% to 50%, the scope of propene carbonate is 5% to 80%, and the scope of diethyl carbonate is 3% to 75%.
14. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 1, ingredient e wherein) free radical starting agent is selected from peroxidating ketone (ketone peroxide), ketal peroxide class (peroxyketal), hydroperoxide kind (hydroperoxide), the two alkanes (dialkyl peroxide) of peroxidating, peroxidating non-annularity alkanes (diacyl peroxide), peroxyesters (peroxy ester) reaches the group that azo-compound (azocompound) is formed.
15. colloidal condition macromolecule electrolyte precursor compositions as claimed in claim 1, ingredient e wherein) free radical starting agent is the two isobutyl group eyeballs (2 of azo, 2-azo-bis-isobutyronitrile, AIBN), phenylazo triphenylmenthane (phenyl-azo-triphenylmethane), peroxidating the 3rd butane (t-butyl peroxide, TBP), peroxidating cumene (cumyl peroxide), acetyl peroxide (acetyl peroxide), dibenzoyl peroxide (benzoyl peroxide, BPO), dilauroyl peroxide (lauroyl peroxide), tributyl hydrogen peroxide (t-butyl hydroperoxide), or tributyl perbenzoate (t-butyl perbenzoate).
16. a macromolecule lithium secondary battery, it comprises:
I) negative pole, but its electrochemistry embeds/moves out alkali metal;
Ii) a positive pole comprises electrochemistry and embeds/move out alkali-metal electrode active material; And
Iii) a kind of negative pole and anodal colloidal condition macromolecule electrolyte of activating, wherein this colloidal condition macromolecule electrolyte is to prepare as each described colloidal condition macromolecule electrolyte precursor compositions in the claim 1 to 15 via heated polymerizable/crosslinked.
17. macromolecule lithium secondary battery as claimed in claim 16, wherein this negative pole comprises a negative pole activating substance, and it is to be selected to comprise: the group that surely mutually spherical carbon (MCMB), vapor deposition carbon fiber (VGCF), CNT (carbon nano-tube) (CNT), coke, carbon black, graphite, acetylene black, carbon fiber and nature of glass carbon and its mixture are formed.
18. macromolecule lithium secondary battery as claimed in claim 16, wherein this negative pole further comprises the fluororesin binder.
19. as macromolecule lithium secondary battery as described in the claim 16, electrode active material that wherein should positive pole is the lithiumation oxide that is selected from vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt and manganese, lithiumation sulfide, lithiumation selenides, and the group that forms of lithiumation tellurides and its mixture.
20. macromolecule lithium secondary battery as claimed in claim 17 wherein should further comprise the fluororesin binder by positive pole.
21. macromolecule lithium secondary battery as claimed in claim 17 wherein should positive pole further comprises and is selected from acetylene black, carbon black, graphite, nickel powder, aluminium powder, titanium valve and stainless steel powder and its mixture is formed one of group conductive additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101158704A CN100424926C (en) | 2005-11-10 | 2005-11-10 | High ion conductivity colloid polyelectrolyte for chargeable and dischargeable polymer secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101158704A CN100424926C (en) | 2005-11-10 | 2005-11-10 | High ion conductivity colloid polyelectrolyte for chargeable and dischargeable polymer secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1964127A CN1964127A (en) | 2007-05-16 |
| CN100424926C true CN100424926C (en) | 2008-10-08 |
Family
ID=38083079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101158704A Active CN100424926C (en) | 2005-11-10 | 2005-11-10 | High ion conductivity colloid polyelectrolyte for chargeable and dischargeable polymer secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100424926C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016086870A1 (en) * | 2014-12-05 | 2016-06-09 | 江苏华东锂电技术研究院有限公司 | Positive electrode composite material and lithium ion battery and preparation method therefor |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101931086B (en) * | 2009-06-25 | 2012-12-12 | 财团法人工业技术研究院 | Interpenetrated reticular proton exchange membrane, forming method thereof and proton exchange membrane fuel cell |
| CN102216391B (en) * | 2009-12-07 | 2013-01-02 | 南京大学 | Composite material with dielectric properties and preparation method thereof |
| KR20160138402A (en) * | 2014-03-28 | 2016-12-05 | 스미또모 세이까 가부시키가이샤 | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and power storage device |
| CN108084403B (en) * | 2016-11-23 | 2020-05-12 | 王復民 | Oligomer polymer and lithium battery |
| TWI682578B (en) * | 2017-12-12 | 2020-01-11 | 財團法人工業技術研究院 | Positive electrode plate and method of forming slurry for positive electrode plate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020090555A1 (en) * | 2001-01-05 | 2002-07-11 | Samsung Sdi Co., Ltd | Polymeric gel electrolyte, lithium battery using the same, and methods of manufacturing the electrolyte and the lithium battery |
| US20030180624A1 (en) * | 2002-03-22 | 2003-09-25 | Bookeun Oh | Solid polymer electrolyte and method of preparation |
| CN1526759A (en) * | 2003-09-23 | 2004-09-08 | 武汉大学 | Lithium ion electrolyte material of polymer gel and prepn of cell therewith |
| CN1571203A (en) * | 2004-04-24 | 2005-01-26 | 大连理工大学 | Method for preparing a complex oxygen ion conductor electrolyte film by quick heat treatment of collosol and gel |
| CN1597766A (en) * | 2004-08-09 | 2005-03-23 | 武汉大学 | Colloidal polymer electrolyte and preparation process thereof |
-
2005
- 2005-11-10 CN CNB2005101158704A patent/CN100424926C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020090555A1 (en) * | 2001-01-05 | 2002-07-11 | Samsung Sdi Co., Ltd | Polymeric gel electrolyte, lithium battery using the same, and methods of manufacturing the electrolyte and the lithium battery |
| US20030180624A1 (en) * | 2002-03-22 | 2003-09-25 | Bookeun Oh | Solid polymer electrolyte and method of preparation |
| CN1526759A (en) * | 2003-09-23 | 2004-09-08 | 武汉大学 | Lithium ion electrolyte material of polymer gel and prepn of cell therewith |
| CN1571203A (en) * | 2004-04-24 | 2005-01-26 | 大连理工大学 | Method for preparing a complex oxygen ion conductor electrolyte film by quick heat treatment of collosol and gel |
| CN1597766A (en) * | 2004-08-09 | 2005-03-23 | 武汉大学 | Colloidal polymer electrolyte and preparation process thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016086870A1 (en) * | 2014-12-05 | 2016-06-09 | 江苏华东锂电技术研究院有限公司 | Positive electrode composite material and lithium ion battery and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1964127A (en) | 2007-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7560194B2 (en) | High ionic conductivity gel polymer electrolyte for rechargeble polymber secondary battery | |
| CN103904295B (en) | Composite electrode material for lithium secondary battery and lithium secondary battery | |
| US8124282B2 (en) | Nonaqueous electrolyte having maleimide additives and secondary cells employing the same | |
| CN106797053B (en) | Gel polymer electrolyte and lithium secondary battery including it | |
| EP3041069B1 (en) | Battery electrode paste composition | |
| KR102551091B1 (en) | Composition for non-aqueous secondary battery adhesive layer, adhesive layer for non-aqueous secondary battery and non-aqueous secondary battery | |
| CN100424926C (en) | High ion conductivity colloid polyelectrolyte for chargeable and dischargeable polymer secondary battery | |
| CN110880620A (en) | Composite solid electrolyte and preparation method thereof, solid lithium battery and preparation method thereof | |
| CN104604014B (en) | Non-aqueous electrolytic solution and the lithium secondary battery for including it | |
| WO2017094252A1 (en) | Composition for non-aqueous secondary cell adhesive layer, adhesive layer for non-aqueous secondary cell, laminate body, and non-aqueous secondary cell | |
| CN111533851A (en) | Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery | |
| CN102569886A (en) | Non-aqueous electrolyte and lithium secondary battery comprising the same | |
| CN109755582A (en) | Lithium ion cell positive polyimide binder and the preparation method and application thereof | |
| CN112366351B (en) | Lithium-supplementing slow-release capsule, electrolyte thereof and lithium ion battery | |
| KR102338192B1 (en) | Binder composition for a non-aqueous secondary battery electrode, a slurry composition for a non-aqueous secondary battery electrode, an electrode for a non-aqueous secondary battery, and a non-aqueous secondary battery | |
| CN106997953A (en) | Lithium battery | |
| CN108808077B (en) | Preparation method of multifunctional gel polymer electrolyte with gradient barium titanate content | |
| CN110518282A (en) | Solid polymer electrolyte, solid lithium ion battery | |
| CN109888369A (en) | A kind of all solid state electrolyte and preparation method thereof and a kind of lithium battery | |
| CN108140885A (en) | Composition for a gel polymer electrolyte and gel polymer electrolyte | |
| CN101471453B (en) | Colloidal condition macromolecule electrolyte precursor composition and secondary battery containing the same | |
| CN110224173B (en) | Self-healing solid polymer electrolyte for lithium battery and preparation method thereof | |
| CN113299982A (en) | In-situ polymerization electrolyte, method for preparing in-situ all-solid-state battery by adopting same and in-situ all-solid-state battery | |
| CN112310471B (en) | Composite solid electrolyte membrane, preparation method thereof and all-solid battery | |
| TW201817781A (en) | Oligomer and lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |