CN109585749A - Lithium ion battery separator and lithium ion battery with it - Google Patents
Lithium ion battery separator and lithium ion battery with it Download PDFInfo
- Publication number
- CN109585749A CN109585749A CN201710908618.1A CN201710908618A CN109585749A CN 109585749 A CN109585749 A CN 109585749A CN 201710908618 A CN201710908618 A CN 201710908618A CN 109585749 A CN109585749 A CN 109585749A
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- China
- Prior art keywords
- ion battery
- lithium ion
- battery separator
- layer
- oxygen
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 59
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 76
- 239000001301 oxygen Substances 0.000 claims abstract description 76
- 238000010521 absorption reaction Methods 0.000 claims abstract description 43
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 239000011358 absorbing material Substances 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims description 42
- -1 4- Aminophenyl amine Chemical class 0.000 claims description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- 230000003078 antioxidant effect Effects 0.000 claims description 22
- 239000003463 adsorbent Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
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- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 3
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000758 substrate Substances 0.000 claims description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
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- 238000005520 cutting process Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- JQQCMCDVLAZJHZ-UHFFFAOYSA-N lithium;methanesulfonic acid Chemical compound [Li].CS(O)(=O)=O JQQCMCDVLAZJHZ-UHFFFAOYSA-N 0.000 description 1
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- CSWFWSPPZMEYAY-UHFFFAOYSA-N octadecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(O)O CSWFWSPPZMEYAY-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000001141 propulsive effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The present invention relates to a kind of lithium ion battery separators, and including the porous matrix layers and oxygen absorption layer being stacked, oxygen absorption layer includes oxygen absorbing materials.The invention further relates to a kind of lithium ion batteries, and including anode, cathode, the lithium ion battery separator and electrolyte being arranged between positive electrode and negative electrode, lithium ion battery separator includes lithium ion battery separator as above, and oxygen absorption layer is close to anode.
Description
Technical field
The present invention relates to battery technology fields, more particularly to lithium ion battery separator and with its lithium ion battery.
Background technique
Diaphragm is one of important component of lithium ion battery.Commercial more extensive diaphragm is monolayer polyethylene at present
Diaphragm (PE), polypropylene diaphragm (PP), tri- layers of composite isolated film of PP/PE/PP and the PP/PE diaphragm with ceramic coated.Diaphragm
Main function be effective isolation positive and negative anodes pole piece, prevent electronics conduction between positive and negative anodes, while guaranteeing that lithium ion can
Effectively and rapidly pass through.Suitable porosity is the key that diaphragm realizes above-mentioned function, and porosity is too small to be unfavorable in electrolyte
The shuttle of lithium ion, causes the internal resistance of cell excessive and cycle life reduces；And porosity effectively cannot block electronics to pass very much greatly
It is defeated, cause self discharge or internal short-circuit.In addition to this, diaphragm is the important component for ensureing lithium ion battery safety, Ren Menpu
It is lithium all over thinking that high temperature lower diaphragm plate collapse (collapse temperature of PE, PP diaphragm is 150 DEG C and 170 DEG C or so respectively) causes internal short-circuit
The main reason for battery thermal runaway.
The safety of battery is played an important role to its high specific energy is given full play to.But diaphragm wants effective guarantee lithium electric
Pond safely, prevent lithium battery thermal runaway, only by prevent internal short-circuit be it is inadequate, especially for high specific energy lithium-ion electric
Pond.From the point of view of " energy conservation and the new-energy automobile Technology Roadmap " issued from the last ten-days period in 2016, the year two thousand twenty China power battery list is arrived
The developing goal of body is that battery specific energy reaches 300Wh/kg, and the service life reaches 4000 times or 10 years.It is foreseeable that the lithium of high-energy-density
The research and development of ion battery will obtain powerful propulsive force.
Therefore, the safety of raising lithium-ion-power cell is needed.
Summary of the invention
Based on this, it is necessary to for the imperfect problem of security performance of existing lithium ion battery, provide a kind of lithium from
Sub- battery diaphragm and lithium ion battery with it.
A kind of lithium ion battery separator, including the porous matrix layers and oxygen absorption layer being stacked, the oxygen absorption layer includes oxygen
Aspiration material.
In one of the embodiments, the oxygen absorption layer with a thickness of 0.2-2 μm.
The partial size of the oxygen absorbing materials is 10-5000nm in one of the embodiments,.
The oxygen absorbing materials include at least one in antioxidant and adsorbent in one of the embodiments,
Kind.
The oxygen absorbing materials include antioxidant and adsorbent in one of the embodiments, and the gas is inhaled
The attached dose of mass percent for accounting for the oxygen absorbing materials is 40-80%.
In one of the embodiments, in the oxygen absorbing materials, the content of the adsorbent is greater than described anti-
The content of oxygen agent.
The adsorbent includes active carbon in one of the embodiments,.
The antioxidant includes p-phenylenediamine, 4- aminophenyl amine, N in one of the embodiments, N '-dimethyl -1,
4 phenylenediamines, N, N '-diphenyl-p-phenylenediamine, N- isopropyl-N '-phenyl-pphenylenediamine, N- (1,3- dimethylbutyl)-N '-
Phenyl-pphenylenediamine, N,-two -2- naphthyl-p-phenylenediamine of N ', diphenylamines, N- phenyl-β-naphthylamine and 4,4 '-dioctyl hexichol
At least one of amine.
It in one of the embodiments, further include the porous ceramic layer being stacked, the porous ceramic layer is coated in institute
The surface of porous matrix layers is stated, the oxygen absorption layer is coated in the surface of the porous matrix layers or the porous ceramic layer.
The porous ceramic layer is set as one layer in one of the embodiments, one coated in the porous matrix layers
A surface, the oxygen absorption layer are coated in another surface of the porous matrix layers.
The porous ceramic layer is set as two layers in one of the embodiments, is respectively coated on the porous matrix layers
Two surfaces, the oxygen absorption layer is set as one layer, the surface coated in any one layer porous ceramic layer.
The porous ceramic layer is set as two layers in one of the embodiments, is respectively coated on the porous matrix layers
Two surfaces, the oxygen absorption layer is set as two layers, is respectively coated on the surface of two layers of porous ceramic layer.
The material particle size of the porous ceramic layer is 10-5000nm in one of the embodiments, with a thickness of 5-20 μm.
A kind of lithium ion battery, including anode, cathode, the lithium ion battery being arranged between the anode and the cathode
Diaphragm and electrolyte, the lithium ion battery separator include lithium ion battery separator as described above, and the oxygen absorption layer is close
The anode.
In one of the embodiments, the material of the anode be cobalt acid lithium, nickel cobalt manganese or nickel cobalt aluminium tertiary cathode material,
Molecular formula is respectively LiCoO2、Li(NixMnyCoz)O2With Li (NixMnyAlz)O2, 0.50≤x < 1.00,0 < y≤0.30,0 <
z≤0.20。
The present invention constitutes the diaphragm of multilayered structure by the way that oxygen absorption layer is laminated on porous matrix layers surface.There is diaphragm to inhale
The ability for receiving oxygen, can be effectively reduced the content of oxygen in battery, greatly reduces oxygen penetration diaphragm in a limited space
The probability to react with the cathode of strong reducing property, so that the battery heat caused by the heat release that effectively avoids reacting because of oxygen is lost
Control, greatly improves the safety of battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the lithium ion battery separator of first embodiment of the invention；
Fig. 2 is the structural schematic diagram of the lithium ion battery separator of second embodiment of the invention；
Fig. 3 is the structural schematic diagram of the lithium ion battery separator of third embodiment of the invention；
Fig. 4 is the structural schematic diagram of the lithium ion battery separator of fourth embodiment of the invention.
Wherein,
Porous matrix layers 100；
Oxygen absorption layer 200；
Porous ceramic layer 300.
Specific embodiment
In order to which the purpose of the present invention, technical solution and technical effect is more clearly understood, below in conjunction with attached drawing to this hair
Bright specific embodiment is described.It should be appreciated that described herein, specific examples are only used to explain the present invention, and does not have to
It is of the invention in limiting.
Referring to Fig. 1, the embodiment of the present invention provides a kind of lithium ion battery separator, including the porous matrix layers being stacked
100 and oxygen absorption layer 200, oxygen absorption layer 200 includes oxygen absorbing materials.
The embodiment of the present invention passes through setting oxygen absorption layer 200, and oxygen absorption layer 200 is coated in the surface of porous matrix layers 100,
Constitute the diaphragm of multilayered structure.Make diaphragm that there is the ability for absorbing oxygen, can be effectively reduced the content of oxygen in battery, greatly
Ground reduces the probability that oxygen penetration diaphragm reacts with the cathode of strong reducing property in a limited space, to effectively avoid because of oxygen
Gas reacts battery thermal runaway caused by heat release, greatly improves the safety of battery.
Porous matrix layers 100 can be selected from the common barrier film base material of lithium ion battery, as polyolefin porous membrane, non-woven fabrics are more
Pore membrane or electrospun membrane.The polyolefin porous membrane can be enumerated as polypropylene porous film, polyethylene porous membrane or polypropylene are porous
The membrane structure to be formed is laminated in film and polyethylene porous membrane.The polyolefin porous membrane can use commercially available lithium ion battery separator,
The separator product that such as Japanese Asahi Chemical Industry Asahi, eastern burning Tonen, space portion Ube, Celgard company, the U.S. produce.The nothing
Woven fabric diaphragm can be enumerated such as polyimide nano-fiber non-woven fabrics, polyethylene terephthalate (PET) nano fiber non-woven
Cloth, cellulose nano-fibrous non-woven fabrics, aramid nano-fiber non-woven fabrics, glass fibre non-woven, nylon nano fiber non-woven fabrics
Or Kynoar (PVDF) nano fiber non-woven fabric.The electrospun membrane can enumerate such as polyimides electrospun membrane, gather to benzene
Dioctyl phthalate second diester electrospun membrane or Kynoar electrospun membrane.Porous matrix layers 100 are for completely cutting off electronics and making lithium ion
Pass through from the micropore of perforated membrane.
The thickness of porous matrix layers 100 is preferably 2-20 μm, and porosity is preferably 20-80%, and aperture is preferably 10-
1500nm, hole density are preferably 1 × 104-1×108cm2。
The thickness of oxygen absorption layer 200 is preferably 0.2-2 μm, and the partial size of the material of oxygen absorption layer 200 is preferably 10-5000nm, with
Make oxygen absorption layer 200 that there is the ability for more preferably absorbing oxygen.
The oxygen absorbing materials of oxygen absorption layer 200 may include at least one of antioxidant and adsorbent.Antioxidant
Oxygen can be removed by way of chemical reaction.Adsorbent can remove oxygen by way of physical absorption.
Preferably, the oxygen absorbing materials of oxygen absorption layer 200 include antioxidant and adsorbent, can be simultaneously with physical absorption
Oxygen is removed with the mode of chemical reaction, adsorbent can also increase the response area of antioxidant, and the two generates collaboration effect
It answers, to make oxygen absorption layer 200 that there is more preferably oxygen uptake ability.The content of adsorbent is preferably greater than the content of antioxidant.
Preferably, it is a, 20%≤a < 100% that adsorbent, which accounts for the mass percent of oxygen absorbing materials, to improve
The fiting effect of adsorbent and antioxidant makes oxygen absorption layer 200 preferably absorb oxygen.It is further preferable that 40%≤a≤
80%, so that the cooperation of adsorbent and antioxidant reaches more preferably effect, so that oxygen absorption layer 200 is had and more preferably absorb oxygen
Power.
Adsorbent can have biggish reference area, such as may include active carbon, carbon black, acetylene black, Ketjen black
At least one of with carbon nanotube, the preferably combination of Ketjen black (Ketjen Black) and carbon nanotube, so that gas is inhaled
Attached dose has the ability for more preferably absorbing oxygen.
The specific type of antioxidant is unlimited, can be anti-for phenolic antioxidant, Phosphorus antioxidant, sulfur type antioxidant and amine
At least one of oxidant etc..
Phenol antioxidant may include quinhydrones, tert-butyl hydroquinone, p methoxy phenol, cresols, tert-butyl catechol,
2,6- di-t-butyls-paracresol, 1,1- bis- (2 '-methyl -4 '-hydroxyl -5 '-tert-butyl-phenyl) butane, 2,2 '-methylene two
(4- methyl-6-tert butyl phenol), 2,6- di-t-butyl -4- (N, N- dimethylamino methyl) phenol, 2,2 '-methylene, two (4- ethyl -
6- tert-butyl phenol), 4,4 '-methylene two (2,6- di-tert-butylphenol), 2,2 '-dihydroxy -3,3 '-two (Alpha-Methyl cyclohexyl) -
5,5 '-dimethyl diphenylmethanes, 2,2 '-ethylidene-two (4,6- di-tert-butylphenol), 4,4 '-thiobis (3- methyl-6-terts
Butylphenol), two (3,5- di-tert-butyl-4-hydroxyl benzyl) sulfide, 4,4 '-two thiobis (2,6- di-tert-butylphenol), 4,4 '-
Three thiobis (2,6- di-tert-butylphenol), 2,4- bis- (just pungent sulfenyl) -6- (4- hydroxyl -3 ', 5 '-di-tert-butyl amidos) -1,
3,5- triazines, N, N '-two (3- (3,5- di-tert-butyl-hydroxy phenyl) propionyl) hydrazine, three (3,5- di-t-butyl -4- hydroxy benzenes
Base) chlorinated isocyanurates, three (3,5- di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, 1,3,5- tri- (4- tert-butyl -3- hydroxyls -
2,6- dimethyl benzyls) chlorinated isocyanurates, bis- -3- of triethylene glycol N- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester,
1,6- hexylene glycol two (3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester), (3- (3, the 5- di-t-butyl -4- of pentaerythrite four
Hydroxy phenyl) propionic ester), hexa-methylene two (3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester), octadecyl 3- (3,
5- di-tert-butyl-hydroxy phenyl) propionic ester, N, N ≡-hexa-methylene two (3,5- di-t-butyl -4- hydroxyls-hydrogen cyanamide), 1,
3,5- trimethyls -2,4, it is 6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, 2,4- bis- ((pungent sulfenyl) methyl)-o-cresol, different
Octyl 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester, four (methylene -3- (3,5- di-tert-butyl-hydroxy phenyl) third
Acid esters) methane and octyl 3,5- di-t-butyl -4- hydroxy benzo propionic ester.
Phosphorus antioxidants may include triphenyl phosphite, three (2,4- di-tert-butyl-phenyl) phosphite esters, the Asia 2,2-
Ethyl two (4,6- di-tert-butylphenol) fluorophosphites, 2,2 '-ethylenes (4,6- di-tert-butyl-phenyl) phosphorous acid monooctyl ester, Asia
Diphenyl phosphate isodecyl base ester, diisodecyl phenyl phosphite, three (nonyl phenyl) phosphite esters, diiso decyl pentaerythrite
Phosphite ester, three (2,4- di-tert-butyl-phenyl) phosphite esters, cyclic annular neopentane four base two (octadecyl) phosphite ester, ring-type
Neopentane four base two (2,4- di-tert-butyl-phenyl) phosphite ester, four base of cyclic annular neopentane, two (2,4- di-t-butyl -4- methylbenzenes
Base) phosphite ester, three (2- tert-butyl -4- (3- tertiary butyl-4-hydroxy -5- methylphenyl-sulfanyl) -5- aminomethyl phenyl) phosphite esters,
Phosphorous acid octyl diphenyl, two (nonyl phenyl) pentaerythritol diphosphites, two (2,4- bis- tertiary phenyl) pentaerythrites two
Phosphite ester, two (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6- tri-tert phenyl)
Pentaerythritol diphosphites, two (2,4- dicumylphenyl) pentaerythritol diphosphites, four (tridecyl) isopropylidenes
Biphenol diphosphites, four (tridecyl) 4,4 '-positive butylidenebis (2- tert-butyl -5- methylphenol) diphosphites,
Six (tridecyl) 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane triphosphite esters, four (2,4- bis- tertiary fourths
Base phenyl) xenyl bis-phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2,2 '-methylene two
(4,6- tert-butyl-phenyl) 2- ethylhexyl phosphite ester.
Sulphur class antioxidant may include dilauryl 3,3- thiodipropionate, myristyl 3,3 '-thio dipropyls
Acid esters, 3,3 '-thiodipropionate of distearyl acyl group, diphenyl sulfide (diphenyl sulfide), diphenyl disulfide and dibutyl sulfide.
Amine antioxidants may include p-phenylenediamine, 4- aminophenyl amine, N, -1,4 phenylenediamine of N '-dimethyl, N, N ' -
Diphenyl-p-phenylenediamine, N- isopropyl-N '-phenyl-pphenylenediamine, N- (1,3- dimethylbutyl)-N '-phenyl-are to benzene two
Amine, N,-two -2- naphthyl-p-phenylenediamine of N ', diphenylamines, N- phenyl-β-naphthylamine and 4,4 '-dioctyl diphenylamines.
Antioxidant is preferably above-mentioned amine antioxidants, it is further preferable that antioxidant is N,-two -2- naphthyl p-phenylenediamine of N '
(DNP), it can make antioxidant that there is more preferably stability and safety, to improve the safety of lithium ion battery.
Ketjen black and carbon nanotube can be separately provided as gas absorption oxidant layer, and DNP can be separately provided as oxygen-getter layer,
And be layered in gas absorption oxidant layer above-mentioned, form oxygen absorption layer.Ketjen black and carbon nanotube can also uniformly be mixed with DNP,
Form oxygen absorption layer.
Fig. 2 to 4 is please referred to, lithium ion battery separator can also include porous ceramic layer 300, and porous ceramic layer 300 coats
On the surface of porous matrix layers 100, the surface or two surfaces of porous matrix layers 100, oxygen absorption layer 200 can be coated in
Surface coated in porous matrix layers 100 or porous ceramic layer 300.The setting of porous ceramic layer 300, can be improved porous substrate
The heat-resisting quantity of layer 100, plays the role of stable porous matrix layers 100, even after porous matrix layers 100 shrink collapse, it is more
Hole ceramic layer 300 also can effectively keep membrane shape, prevent extensive internal short-circuit from occurring, further increase the safety of battery.
Preferably, porous ceramic layer 300 with a thickness of 5-20 μm, the partial size of the material of porous ceramic layer 300 is 1-
5000nm.The material of porous ceramic layer 300 includes inorganic ceramic particle, and inorganic ceramic particle can be Al2O3, SiO2,TiO2With
ZrO2One of or a variety of, preferably Al2O3.The material of porous ceramic layer 300 can also include binder, and binder can be with
It is sub- for Kynoar, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, polyamides
One of amine, polyethylene oxide, cellulose acetate and polyvinyl alcohol are a variety of, preferably Kynoar.Preferably, it bonds
The mass percent that agent accounts for porous ceramic layer 300 is 0.1-5%.
Porous ceramic layer 300 can be set to one layer, and coated in porous matrix layers 100 a surface, oxygen absorption layer 200 is set
It is set to one layer, another surface coated in porous matrix layers 100.
Preferably, porous ceramic layer 300 is set as two layers, is respectively coated on two surfaces of porous matrix layers 100.Oxygen uptake
Layer 200 can be set to one layer, coat on the surface of wherein one layer of porous ceramic layer 300；Oxygen absorption layer 200 is preferably arranged to two
Layer, is respectively coated on the surface of two layers of porous ceramic layer 300.
The embodiment of the present invention also provides a kind of manufacturing method of lithium ion battery separator, comprising the following steps:
S100 provides porous matrix layers 100；
S200 provides alumina powder and Kynoar, mixes and is dissolved in N- methyl pyrrole network alkanone, Ultrasonic Pulverization
And stirring, form ceramic coated slurry；
Ceramic coated slurry is coated to the surface of porous matrix layers 100 and drying, forms porous ceramic layer 300 by S300；
S400 provides DNP, Ketjen black, carbon nanotube and binder, after mixing, coating to porous ceramic layer 300 or
The surfaces of porous matrix layers 100 and drying.
The embodiment of the present invention also provides a kind of lithium ion battery, including anode, cathode, is arranged between positive electrode and negative electrode
Lithium ion battery separator and electrolyte, lithium ion battery separator lithium ion battery separator as above, oxygen absorption layer 200 is close to just
Pole.
The electrolyte includes solvent and the lithium salts solute for being dissolved in solvent, which can be selected from cyclic carbonate, chain carbonic acid
One of ester, ring-type ethers, chain ethers, nitrile and amides are a variety of, such as ethylene carbonate, propene carbonate, carbonic acid
Diethylester, dimethyl carbonate, methyl ethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, two
Ether, acetonitrile, propionitrile, methyl phenyl ethers anisole, butyrate, glutaronitrile, dintrile, gamma-butyrolacton, gamma-valerolactone, tetrahydrofuran, 1,2-
Dimethoxy-ethane and one of acetonitrile and dimethylformamide are a variety of.The lithium salts solute can be selected from lithium chloride (LiCl),
Lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), methanesulfonic acid lithium (LiCH3SO3), trifluoromethanesulfonic acid lithium (LiCF3SO3)、
Hexafluoroarsenate lithium (LiAsF6), lithium perchlorate (LiClO4) and one of di-oxalate lithium borate (LiBOB) or a variety of.
The anode may include plus plate current-collecting body and positive electrode material layer, and the plus plate current-collecting body is for supporting the positive electrode material layer simultaneously
Electric current is conducted, shape can be paillon or netted.The material of the plus plate current-collecting body can be selected from aluminium, titanium or stainless steel.The anode
Material layer is arranged on a plus plate current-collecting body at least surface.The positive electrode material layer includes positive electrode active materials, further be may be selected
Include conductive agent and binder.Conductive agent and binder can uniformly be mixed with positive electrode active materials.The material of the anode
Material is cobalt acid lithium, nickel cobalt manganese or nickel cobalt aluminium tertiary cathode material, and molecular formula is respectively LiCoO2(cobalt acid lithium), Li (NixMnyCoz)
O2(nickel manganese cobalt tertiary cathode) and Li (NixMnyAlz)O2(nickel manganese aluminium tertiary cathode), 0.50≤x < 1.00,0 < y≤0.30,0
Z≤0.20 < etc..
The cathode may include negative current collector and negative electrode material layer, and the negative current collector is for supporting the negative electrode material layer simultaneously
Electric current is conducted, shape can be paillon or netted.The material of the negative current collector can be selected from copper, nickel or stainless steel.The cathode
Material layer is arranged on a negative current collector at least surface.The negative electrode material layer includes negative electrode active material, further be may be selected
Include conductive agent and binder.Conductive agent and binder can uniformly be mixed with negative electrode active material.The negative electrode active
Material can be graphite, acetylene black, microballon carbon, carbon fiber, carbon nanotube or cracking carbon etc..
The lithium ion battery separator and lithium ion battery of the embodiment of the present invention, porous ceramic layer 300 are coated in porous substrate
The surface of layer 100, oxygen absorption layer 200 are coated in the surface of porous matrix layers 100 or the surface of porous ceramic layer 300, not only can be with
Battery thermal runaway caused by collapsing because of porous matrix layers 100 effectively is prevented, can also absorb the oxygen that positive polar decomghtion generates, is prevented
Only anode produces thermal runaway caused by oxygen, has double protection functions, can prevent the generation of battery thermal runaway, pole in all directions
The earth improves the safety in utilization of lithium ion battery, is conducive to the advantage that lithium ion battery gives full play to high specific energy.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (15)
1. a kind of lithium ion battery separator, which is characterized in that including the porous matrix layers and oxygen absorption layer being stacked, the oxygen uptake
Layer includes oxygen absorbing materials.
2. lithium ion battery separator according to claim 1, which is characterized in that the oxygen absorption layer with a thickness of 0.2-2 μm.
3. lithium ion battery separator according to claim 1, which is characterized in that the partial size of the oxygen absorbing materials is
10-5000nm。
4. lithium ion battery separator according to claim 1, which is characterized in that the oxygen absorbing materials include antioxidant
And at least one of adsorbent.
5. lithium ion battery separator according to claim 4, which is characterized in that the oxygen absorbing materials include antioxidant
And adsorbent, the mass percent that the adsorbent accounts for the oxygen absorbing materials is 40-80%.
6. lithium ion battery separator according to claim 4, which is characterized in that in the oxygen absorbing materials, the gas
The content of body adsorbent is greater than the content of the antioxidant.
7. lithium ion battery separator according to claim 4, which is characterized in that the adsorbent includes active carbon.
8. lithium ion battery separator according to claim 4, which is characterized in that the antioxidant includes p-phenylenediamine, 4-
Aminophenyl amine, N, -1,4 phenylenediamine of N '-dimethyl, N, N '-diphenyl-p-phenylenediamine, N- isopropyl-N '-phenyl-are to benzene two
Amine, N- (1,3- dimethylbutyl)-N '-phenyl-pphenylenediamine, N,-two -2- naphthyl-p-phenylenediamine of N ', diphenylamines, N- phenyl -
At least one of beta-naphthylamine and 4,4 '-dioctyl diphenylamines.
9. lithium ion battery separator according to any one of claims 1 to 8, which is characterized in that further include being stacked
Porous ceramic layer, the porous ceramic layer are coated in the surface of the porous matrix layers, and the oxygen absorption layer is coated in described porous
The surface of substrate layer or the porous ceramic layer.
10. lithium ion battery separator according to claim 9, which is characterized in that the porous ceramic layer is set as one layer,
A surface coated in the porous matrix layers, the oxygen absorption layer are coated in another surface of the porous matrix layers.
11. lithium ion battery separator according to claim 9, which is characterized in that the porous ceramic layer is set as two layers,
Two surfaces of the porous matrix layers are respectively coated on, the oxygen absorption layer is set as one layer, and it is described more to be coated in any one layer
The surface of hole ceramic layer.
12. lithium ion battery separator according to claim 9, which is characterized in that the porous ceramic layer is set as two layers,
Be respectively coated on two surfaces of the porous matrix layers, the oxygen absorption layer is set as two layers, be respectively coated on two layers it is described more
The surface of hole ceramic layer.
13. lithium ion battery separator according to claim 9, which is characterized in that the material particle size of the porous ceramic layer
For 10-5000nm, with a thickness of 5-20 μm.
14. a kind of lithium ion battery, which is characterized in that including anode, cathode, be arranged between the anode and the cathode
Lithium ion battery separator and electrolyte, the lithium ion battery separator include such as the described in any item lithiums of claim 1 to 13
Ion battery diaphragm, the oxygen absorption layer is close to the anode.
15. lithium ion battery according to claim 14, which is characterized in that the material of the anode is cobalt acid lithium, nickel cobalt
Manganese or nickel cobalt aluminium tertiary cathode material, molecular formula are respectively LiCoO2、Li(NixMnyCoz)O2With Li (NixMnyAlz)O2, 0.50
1.00,0 < y≤0.30 of≤x <, 0 z≤0.20 <.
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