CN109950459A - A kind of lithium ion battery separator of richness lithium - Google Patents
A kind of lithium ion battery separator of richness lithium Download PDFInfo
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- CN109950459A CN109950459A CN201910234299.XA CN201910234299A CN109950459A CN 109950459 A CN109950459 A CN 109950459A CN 201910234299 A CN201910234299 A CN 201910234299A CN 109950459 A CN109950459 A CN 109950459A
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- lithium
- ion battery
- lithium ion
- richness
- diaphragm
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 113
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 210000002469 basement membrane Anatomy 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 22
- -1 ester compounds Chemical class 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229910017083 AlN Inorganic materials 0.000 claims description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 210000004379 membrane Anatomy 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical group CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 8
- 159000000002 lithium salts Chemical class 0.000 abstract description 8
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 239000013589 supplement Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 150000002642 lithium compounds Chemical class 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 16
- 239000011268 mixed slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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 present invention relates to a kind of lithium ion battery separators of rich lithium, and by the way that rich lithium coating is arranged in diaphragm at least side, the lithium salts for including in rich lithium coating can provide in use stable lithium ion source to battery.During first charge-discharge, the lithium salts in rich lithium layer, which is dissolved in electrolyte, releases lithium ion, the consumption of lithium ion when supplement SEI film is formed；The SEI film on graphite cathode surface can be made to quickly form and reach stable state simultaneously, improve the quality of SEI film, reduce the impedance of SEI film；In use, the lithium salts in rich lithium layer is gradually released lithium ion battery, is kept the concentration of lithium salts in electrolyte, is improved the cycle life of battery；Lithium in the present invention exists in a manner of lithium compound; the influence for being unfavorable for large-scale production using lithium metal bring security risk and working condition harshness is avoided, using the simple process of the rich lithium layer diaphragm of this method production; it is friendly to production environment, easy, mass production easy to accomplish.
Description
Technical field
The invention belongs to field of batteries, and in particular to a kind of lithium ion battery separator of richness lithium.
Background technique
Lithium ion battery becomes application range most due to the advantage with high voltage, high-energy density and long circulation life
One of wide secondary cell.But with portable electronic device micromation, long standby continuous development and electric bicycle,
Electric car etc. is high-power, high-energy device enabling, proposes to the energy density of the lithium ion battery as accumulation power supply
Increasingly higher demands.
It, all can be due to the shape of solid electrolyte film (SEI film) during the initial charge of battery for negative electrode tab
At and consume part lithium, cause the loss of anode material of lithium therefrom, to reduce the capacity of battery, cause first charge discharge efficiency
It reduces.This with alloy material (such as silicon alloy and tin alloy) be active material negative electrode tab in show particularly evident.
In order to reduce the reduction of the irreversible capacity bring battery capacity due to battery during first charge-discharge,
There are some solutions of some patent literature reports.Such as the Chinese patent application of Publication No. CN102916165A mention by
In an inert atmosphere, it is reduced the lithium ion in organolithium solution in negative electrode tab surface organolithium spray solution or dropwise addition
It at lithium metal and is embedded in negative electrode tab, then dries negative electrode tab.
For another example it is used application No. is the Japanese patent application of JP1996027910 and metal lithium sheet is covered on negative electrode tab surface,
Then battery is made in winding, and the method that electrolyte is then perfused prepares lithium ion battery.Although this method, which can also play, mends lithium
Effect, however the amount of lithium that negative electrode tab can absorb is far smaller than the lithium of metal lithium sheet offer, therefore will cause the unevenness of embedding lithium
It is even, and lead to the deformation of pole piece, and analysis lithium is also easy to appear in following cycle.
For another example lithium metal powder is covered on diaphragm by binder by the Chinese patent application of publication number CN105932206A
On, then in coated ceramic layer.
Although above-mentioned each method can play the role of mending lithium, the supplement source of lithium is all the lithium metal mended in lithium,
Since lithium metal activity is very strong, lithium metal powder is easy to contact with external environment, causes security risk；And it is answered in actual production
In, the requirement to equipment, environment is very harsh, and large-scale production is difficult.
Summary of the invention
It in order to solve the problems in the existing technology, should the present invention provides a kind of lithium ion battery separator of rich lithium
The rich lithium layer of diaphragm can provide stable lithium ion source to battery, and environmentally friendly.Lithium in rich lithium layer is with compound
Form exist, avoid lithium metal powder bring security risk, guarantee production safety, entire manufacturing process simple process is held
It easily accomplishes scale production, the content of lithium can be adjusted by the thickness and proportion of rich lithium layer in rich lithium layer, pass through letter
Just method realizes the purpose for mend to battery lithium.
Specifically, the lithium ion battery separator of the richness lithium, including diaphragm basement membrane, in at least side of the diaphragm basement membrane
Coated with rich lithium coating；
The diaphragm basement membrane is selected from polyolefins diaphragm；
Preferably, the polyolefins diaphragm is selected from polyethylene (PE) diaphragm, polypropylene (PP) diaphragm and polyethylene-
Any one in polypropylene composite film；
Preferably, the diaphragm basement membrane with a thickness of 6-100 μm；Most preferably, the diaphragm basement membrane thickness is 9-
30μm；
The richness lithium coating includes lithium compound, ceramic powder, polyacrylacid ester compounds, binder；
Preferably, each ingredient percent is as follows in the rich lithium coating: lithium-containing compound 30-90%, ceramics
Powder 0-40%, polyacrylacid ester compounds 5-30%, binder 5-30%；
The lithium-containing compound is selected from one of lithium carbonate, dioxalic acid lithium borate or a variety of, preferably lithium carbonate；
The ceramic powder be selected from aluminum oxide, silica, titanium dioxide, stannic oxide, zinc oxide, calcium oxide,
One of magnesia, calcium carbonate, barium carbonate, barium sulfate, barium titanate, aluminium nitride, magnesium nitride are a variety of；
The polyacrylacid ester compounds are selected from polymethyl methacrylate, polyethyl methacrylate, poly- methyl-prop
One of olefin(e) acid butyl ester is a variety of；
The binder is selected from one of nitrile rubber, butadiene-styrene rubber, polyvinyl alcohol or a variety of；
It is described richness lithium coating with a thickness of 2-50 μm, preferably 2-8 μm；
Further, the lithium ion battery separator of the rich lithium, preparation method include the following steps:
(1) prepared by slurry: solvent is added in lithium-containing compound, ceramic powder, polyacrylacid ester compounds, binder
In, it is uniformly mixed, obtains mixture paste；
(2) in coating on base films mixed slurry, by high temperature drying to get.
The present invention has the following technical effect that compared with the existing technology
(1) present invention in view of the deficiencies of the prior art, by being arranged rich lithium coating in diaphragm at least side, in rich lithium coating
The lithium salts for including can provide in use stable lithium ion source to battery.During first charge-discharge, rich lithium layer
In lithium salts be dissolved in electrolyte and release lithium ion, the consumption of lithium ion when supplement SEI film formation；Graphite can be made negative simultaneously
The SEI film of pole surface quickly forms and reaches stable state, improves the quality of SEI film, reduces the impedance of SEI film；Lithium-ion electric
In use, the lithium salts in rich lithium layer is gradually released in pond, keeps the concentration of lithium salts in electrolyte, improves battery
Cycle life；
(2) lithium in the rich lithium coating of the present invention exists in a manner of lithium compound, avoids tradition benefit lithium mode and uses gold
Belong to lithium bring security risk and working condition harshness is unfavorable for the influence of large-scale production, using what is made in this method
The simple process that rich lithium layer diaphragm is realized, friendly to production environment, easy, mass production easy to accomplish；
(3) the rich lithium layer of diaphragm of the present invention can provide stable lithium ion source, entire manufacturing process technique letter to battery
Just, large-scale production easy to accomplish, the content of lithium can be adjusted by the thickness and proportion of rich lithium layer in rich lithium layer, be led to
It crosses short-cut method and realizes the purpose for mend to battery lithium.
Detailed description of the invention
Fig. 1 is the lithium ion battery separator structural schematic diagram of the invention containing single layer richness lithium coating；
Fig. 2 is lithium ion battery separator structural schematic diagram of the present invention containing the double-deck rich lithium coating；
Wherein 101, diaphragm basement membrane；102, rich lithium coating.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
As shown in Figure of description Fig. 1, a kind of lithium ion battery separator of richness lithium, including diaphragm basement membrane 101, the diaphragm
Basement membrane be polypropylene (PP) diaphragm, diaphragm basement membrane 101 with a thickness of 16 μm；It is rich that 4 μ m-thicks are coated in the side of diaphragm basement membrane 101
Lithium coating 102, the richness lithium coating 102 are composed of the following components:
Carbonic acid powder for lithium (partial size is 5 μm) 12g；
Aluminum oxide powder (5 μm of partial size) 55g；
Polymethyl methacrylate (molecular weight is 60,000) 18g；
Nitrile rubber (acrylonitrile content 15%) 15g；
The lithium ion battery separator of the richness lithium, preparation method include the following steps:
(1) mixed slurry is prepared: by the carbonic acid powder for lithium of 32g, 35g aluminum oxide powder, 18g poly-methyl methacrylate
Ester, 15g nitrile rubber are added in 100g nmp solvent, are uniformly mixed and obtain mixed slurry (using high speed disperser)；
(2) mixed slurry is coated on PP film and (uses intaglio press), ultimately form 4 μm in the side of diaphragm basement membrane
Rich lithium coating to get.
Further, using the diaphragm of above-mentioned preparation, being assemblied in positive electrode is ternary (523 type), and negative electrode material is artificial
In the lithium ion battery of graphite, wherein electrolyte are as follows: LiPF6/EC+DEC+DEC (volume ratio 1:1:1) prepares 5Ah lamination Soft Roll
Battery.
Embodiment 2
As shown in Figure of description Fig. 2, a kind of lithium ion battery separator of richness lithium, including diaphragm basement membrane 101, the diaphragm
Basement membrane be polyethylene (PE) diaphragm, diaphragm basement membrane with a thickness of 20 μm；2 μ m-thicks have been respectively coated in the two sides of diaphragm basement membrane 101
Rich lithium coating 102, the richness lithium coating 102 are composed of the following components:
Carbonic acid powder for lithium (partial size is 5 μm) 18g；
Aluminum oxide powder (5 μm of partial size) 40g；
Polymethyl methacrylate (molecular weight is 60,000) 15g；
Nitrile rubber (acrylonitrile content 27%) 27g；
The lithium ion battery separator of the richness lithium, preparation method include the following steps:
(1) mixed slurry is prepared: by the carbonic acid powder for lithium of 58g, 20g aluminum oxide powder, 10g poly-methyl methacrylate
Ester, 12g nitrile rubber are added in 100g nmp solvent, are uniformly mixed and obtain mixed slurry (using high speed disperser)；
(2) mixed slurry is coated on PE film and (uses intaglio press), ultimately form 2 μm of rich lithiums in the two sides of basement membrane
Layer to get.
Further, using the diaphragm of above-mentioned preparation；Being assemblied in positive electrode is ternary (523 type), and negative electrode material is artificial
In the lithium ion battery of graphite, wherein electrolyte are as follows: LiPF6/EC+DEC+DEC (volume ratio 1:1:1) prepares 5Ah lamination Soft Roll
Battery.
Embodiment 3
As shown in Figure of description Fig. 2, a kind of lithium ion battery separator of richness lithium, including diaphragm basement membrane 101, the diaphragm
Basement membrane be polyethylene (PE) diaphragm, diaphragm basement membrane with a thickness of 20 μm；2 μ m-thicks have been respectively coated in the two sides of diaphragm basement membrane 101
Rich lithium coating 102, the richness lithium coating 102 are composed of the following components:
Carbonic acid powder for lithium (partial size is 5 μm) 10g；
Aluminum oxide powder (5 μm of partial size) 60g；
Polymethyl methacrylate (molecular weight is 60,000) 20g；
Nitrile rubber (acrylonitrile content 10%) 10g；
The lithium ion battery separator of the richness lithium, preparation method include the following steps:
(1) mixed slurry is prepared: by the carbonic acid powder for lithium of 70g, 10g aluminum oxide powder, 7g poly-methyl methacrylate
Ester, 13g nitrile rubber are added in 100g nmp solvent, are uniformly mixed and obtain mixed slurry (using high speed disperser)；
(2) mixed slurry is coated on PE film and (uses intaglio press), ultimately form 2 μm of rich lithiums in the two sides of basement membrane
Layer to get.
Further, using the diaphragm of above-mentioned preparation；Being assemblied in positive electrode is ternary (523 type), and negative electrode material is artificial
In the lithium ion battery of graphite, wherein electrolyte are as follows: LiPF6/EC+DEC+DEC (volume ratio 1:1:1) prepares 5Ah lamination Soft Roll
Battery.
Comparative example 1
A kind of lithium ion battery separator, including diaphragm basement membrane 101, the diaphragm basement membrane are polypropylene (PP) diaphragm, diaphragm
Basement membrane 101 with a thickness of 16 μm；
Further, using above-mentioned diaphragm, being assemblied in positive electrode is ternary (523 type), negative electrode material artificial graphite
In lithium ion battery, wherein electrolyte are as follows: LiPF6/EC+DEC+DEC (volume ratio 1:1:1) prepares 5Ah lamination soft-package battery.
Comparative example 2
A kind of lithium ion battery separator, including diaphragm basement membrane 101, the diaphragm basement membrane are polypropylene (PE) diaphragm, diaphragm
Basement membrane 101 with a thickness of 20 μm；
Further, using above-mentioned diaphragm, being assemblied in positive electrode is ternary (523 type), negative electrode material artificial graphite
In lithium ion battery, wherein electrolyte are as follows: LiPF6/EC+DEC+DEC (volume ratio 1:1:1) prepares 5Ah lamination soft-package battery.
Verify example
Lithium ion battery carries out cycle performance test (1.0C/1.0C multiplying power, temperature in Example 1-3, comparative example 1-2
25±3℃)。
(1) first charge-discharge efficiency is tested
It is charged to 3.4V with 0.1C continuous current, battery is melted into 3.95V with 0.2C constant-current charge, and is evacuated
0.2C constant-current constant-voltage charging calculates its total charging capacity to 4.2V, cut-off current 0.02C after sealing, then is discharged with 0.2C
To 3.0V, discharge capacity, discharging efficiency=discharge capacity/charging total capacity * 100% are obtained.
Test result is as follows shown in table 1:
The first charge-discharge efficiency of 1 lithium ion battery of table
| Project | First charge-discharge efficiency |
| Embodiment 1 | 91.2% |
| Embodiment 2 | 91.6% |
| Embodiment 3 | 91.5% |
| Comparative example 1 | 87.4% |
| Comparative example 2 | 88.8% |
(2) battery DC inner walkway
A) with 0.2C5A constant current, 4.2V pressure limiting, standard charging is carried out to lithium ion battery；
B) with 0.2C5A constant-current discharge to 10%DOD；
C) constant-current charge (generally 1C5A) is carried out to battery with high current；
D) step a)~c is repeated), each depth of discharge increases by 10%, until depth of discharge is 90%；
E) battery is made to discharge completely to final voltage 2.5V with 0.2C5A constant-current discharge.
Test result is as follows shown in table 2:
2 cycle performance of lithium ion battery of table
| Project | Cycle performance (500 weeks conservation rates) | Battery DC internal resistance (m Ω) |
| Embodiment 1 | 90.2% | 4.3 |
| Embodiment 2 | 92.6% | 3.8 |
| Embodiment 3 | 89.5% | 4.8 |
| Comparative example 1 | 85.4% | 5.5 |
| Comparative example 2 | 87.8% | 5.1 |
By upper Tables 1 and 2 it is found that the lithium of the lithium ion battery separator of the preparation-obtained rich lithium of 1-3 of the embodiment of the present invention
The cycle performance and DC internal resistance rate of ion battery be significantly better than that comparative example 1-2 it is preparation-obtained without rich lithium coating lithium from
The lithium ion battery of sub- battery diaphragm.
Its reason is: lithium battery forms SEI film consumption lithium ion in cyclic process, so that the internal resistance of cell increases, lithium
The reduction of ion transportation, and having rich lithium layer to discharge in time and supplementing charging and discharging lithium battery process for rich lithium layer membrane surface disappears
The lithium ion of consumption improves the cycle performance of battery.
Rich lithium diaphragm is respectively arranged with rich lithium layer in the one or both sides of basement membrane in the present invention, on the one hand can improve lithium ion
The stability of SEI film when Battery formation reduces the impedance of SEI film, the lithium that supplement SEI film loses when being formed；On the other hand, it is following
During ring, stablize electrolyte component, supplement the lithium of consumption, improves battery cycle life.
Claims (10)
1. a kind of lithium ion battery separator of richness lithium, including diaphragm basement membrane, which is characterized in that at least the one of the diaphragm basement membrane
Side is coated with rich lithium coating, and lithium-containing compound, ceramic powder, polyacrylacid ester compounds are contained in the richness lithium coating and are glued
Mixture.
2. the lithium ion battery separator of richness lithium according to claim 1, which is characterized in that the lithium-containing compound is selected from carbon
One of sour lithium, dioxalic acid lithium borate are a variety of.
3. the lithium ion battery separator of richness lithium according to claim 1, which is characterized in that the ceramic powder is selected from three oxygen
Change two aluminium, silica, titanium dioxide, stannic oxide, zinc oxide, calcium oxide, magnesia, calcium carbonate, barium carbonate, barium sulfate,
One of barium titanate, aluminium nitride, magnesium nitride are a variety of.
4. the lithium ion battery separator of richness lithium according to claim 1, which is characterized in that the polyacrylate chemical combination
Object is selected from one of polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate or a variety of.
5. the lithium ion battery separator of richness lithium according to claim 1, which is characterized in that the binder is selected from butyronitrile rubber
One of glue, butadiene-styrene rubber, polyvinyl alcohol are a variety of.
6. the lithium ion battery separator of richness lithium according to claim 1, which is characterized in that the diaphragm basement membrane is selected from polyene
Hydro carbons diaphragm, with a thickness of 6-100 μm, preferably 9-30 μm.
7. the lithium ion battery separator of richness lithium according to claim 6, which is characterized in that the polyolefins diaphragm is selected from
Any one in polyethylene diagrams, polypropylene diaphragm and polyethylene-polypropylene composite membrane.
8. the lithium ion battery separator of richness lithium according to claim 1, which is characterized in that each ingredient in the richness lithium coating
Mass percent is as follows: lithium-containing compound 30-90%, ceramic powder 0-40%, polyacrylacid ester compounds 5-30%, bonding
Agent 5-30%.
9. it is according to claim 1 richness lithium lithium ion battery separator, which is characterized in that it is described richness lithium coating with a thickness of
2-50μm。
10. the lithium ion battery separator of richness lithium according to claim 9, which is characterized in that the thickness of the richness lithium coating
It is 2-8 μm.
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| CN201910234299.XA CN109950459A (en) | 2019-03-26 | 2019-03-26 | A kind of lithium ion battery separator of richness lithium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110556493A (en) * | 2019-08-13 | 2019-12-10 | 中国科学院化学研究所 | Functional composite diaphragm of lithium/sodium secondary battery and preparation method thereof |
| CN111540870A (en) * | 2020-05-08 | 2020-08-14 | 中航锂电技术研究院有限公司 | Diaphragm, preparation method and lithium ion battery |
| CN112234314A (en) * | 2020-09-28 | 2021-01-15 | 佛山市金辉高科光电材料股份有限公司 | Composite slurry, lithium battery diaphragm and preparation method and application of lithium battery diaphragm |
| CN112467304A (en) * | 2020-11-30 | 2021-03-09 | 江苏厚生新能源科技有限公司 | Organic fiber reinforced polyethylene lithium battery diaphragm and preparation method thereof |
| CN112635915A (en) * | 2020-12-21 | 2021-04-09 | 合肥国轩高科动力能源有限公司 | Modified diaphragm for metal lithium cathode and preparation method and application thereof |
| CN113851786A (en) * | 2021-06-03 | 2021-12-28 | 中材锂膜有限公司 | Pre-lithiation composite diaphragm and preparation method thereof |
| CN113889676A (en) * | 2020-07-03 | 2022-01-04 | 北京好风光储能技术有限公司 | Repairing and regenerating method for lithium-containing battery |
| CN114006130A (en) * | 2021-09-27 | 2022-02-01 | 河北金力新能源科技股份有限公司 | High-heat-resistance lithium-supplementing diaphragm slurry, diaphragm and lithium battery |
| WO2022041929A1 (en) * | 2020-08-28 | 2022-03-03 | 重庆金美新材料科技有限公司 | Lithium replenishing diaphragm and preparation method for lithiumreplenishing diaphragm |
| CN114597591A (en) * | 2022-05-10 | 2022-06-07 | 四川新能源汽车创新中心有限公司 | Lithium battery diaphragm and preparation method and application thereof |
| CN115051110A (en) * | 2022-06-28 | 2022-09-13 | 楚能新能源股份有限公司 | Lithium supplement composite isolation membrane, preparation method thereof, lithium supplement device and application |
| CN115051109A (en) * | 2022-06-28 | 2022-09-13 | 楚能新能源股份有限公司 | Lithium-supplementing composite isolating membrane and preparation method and application thereof |
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| CN110556493A (en) * | 2019-08-13 | 2019-12-10 | 中国科学院化学研究所 | Functional composite diaphragm of lithium/sodium secondary battery and preparation method thereof |
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| CN112234314B (en) * | 2020-09-28 | 2023-05-05 | 佛山市金辉高科光电材料股份有限公司 | Composite slurry, lithium battery separator and preparation method and application of lithium battery separator |
| CN112467304B (en) * | 2020-11-30 | 2022-08-05 | 江苏厚生新能源科技有限公司 | Organic fiber reinforced polyethylene lithium battery diaphragm and preparation method thereof |
| CN112467304A (en) * | 2020-11-30 | 2021-03-09 | 江苏厚生新能源科技有限公司 | Organic fiber reinforced polyethylene lithium battery diaphragm and preparation method thereof |
| CN112635915A (en) * | 2020-12-21 | 2021-04-09 | 合肥国轩高科动力能源有限公司 | Modified diaphragm for metal lithium cathode and preparation method and application thereof |
| WO2022188355A1 (en) * | 2021-03-12 | 2022-09-15 | 天津市捷威动力工业有限公司 | Composite lithium compensation diaphragm and secondary battery comprising same |
| CN113851786A (en) * | 2021-06-03 | 2021-12-28 | 中材锂膜有限公司 | Pre-lithiation composite diaphragm and preparation method thereof |
| CN114006130A (en) * | 2021-09-27 | 2022-02-01 | 河北金力新能源科技股份有限公司 | High-heat-resistance lithium-supplementing diaphragm slurry, diaphragm and lithium battery |
| CN114597591A (en) * | 2022-05-10 | 2022-06-07 | 四川新能源汽车创新中心有限公司 | Lithium battery diaphragm and preparation method and application thereof |
| CN114597591B (en) * | 2022-05-10 | 2022-08-12 | 四川新能源汽车创新中心有限公司 | Lithium battery diaphragm and preparation method and application thereof |
| CN115051110A (en) * | 2022-06-28 | 2022-09-13 | 楚能新能源股份有限公司 | Lithium supplement composite isolation membrane, preparation method thereof, lithium supplement device and application |
| CN115051109A (en) * | 2022-06-28 | 2022-09-13 | 楚能新能源股份有限公司 | Lithium-supplementing composite isolating membrane and preparation method and application thereof |
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