CN102290597A - Safe-type high-energy density lithium-ion battery - Google Patents
Safe-type high-energy density lithium-ion battery Download PDFInfo
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- CN102290597A CN102290597A CN2011102178679A CN201110217867A CN102290597A CN 102290597 A CN102290597 A CN 102290597A CN 2011102178679 A CN2011102178679 A CN 2011102178679A CN 201110217867 A CN201110217867 A CN 201110217867A CN 102290597 A CN102290597 A CN 102290597A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002033 PVDF binder Substances 0.000 claims abstract description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006229 carbon black Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000004760 aramid Substances 0.000 claims abstract description 13
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 13
- 230000002745 absorbent Effects 0.000 claims abstract description 12
- 239000002250 absorbent Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 239000000835 fiber Substances 0.000 claims abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 9
- 238000007731 hot pressing Methods 0.000 claims abstract description 5
- 230000004888 barrier function Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910013716 LiNi Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- PQYORWUWYBPJLQ-UHFFFAOYSA-N buta-1,3-diene;sulfurous acid Chemical compound C=CC=C.OS(O)=O PQYORWUWYBPJLQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- XMNQCSOOUOJOLR-UHFFFAOYSA-N ethyl methyl hydrogen phosphate Chemical compound CCOP(O)(=O)OC XMNQCSOOUOJOLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000004513 sizing Methods 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 abstract 1
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- 229910002993 LiMnO2 Inorganic materials 0.000 abstract 1
- 229910003005 LiNiO2 Inorganic materials 0.000 abstract 1
- 229910013677 LiNixMnyCo1-x-yO2 Inorganic materials 0.000 abstract 1
- 229910013686 LiNixMnyCo1−x−yO2 Inorganic materials 0.000 abstract 1
- 238000013459 approach Methods 0.000 abstract 1
- 229910021383 artificial graphite Inorganic materials 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229920001084 poly(chloroprene) Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910018871 CoO 2 Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Cell Separators (AREA)
Abstract
The invention discloses a safe-type high-energy density lithium-ion battery, which comprises a cathode plate, an anode plate, a diaphragm and an electrolyte. The cathode plate comprises the following sizing agents in percentage by mass: 92 to 96 percent of LiNixMnyCo1-x-yO2, 0.1 to 3 percent of oxygen absorbent, 1 to 3.5 percent of carbon black and 2 to 3.5 percent of polyvinylidene fluoride (PVDF), wherein x is more than and equal to 1 and less than and equal to 9, and y is more than and equal to 1 and less than and equal to 9; the anode plate comprises the following sizing agents in percentage by mass: 91 to 95 percent of graphite, 1 to 3.5 percent of carbon black, 1.2 to 2.5 percent of Carboxyl methyl Cellulose (CMC) and 1 to 3 percent of Neoprene (SBR); and the diaphragm of the battery is formed by hot-pressing compounding polyolefin porous films and aromatic polyamide fiber. In the lithium-ion battery, the cathode material integrates the advantages of LiCoO2, LiMnO2 and LiNiO2 and has the characteristics of high electrochemical capacity and good cycle performance; when upper-limit charging voltage is more than 4.3 to 4.5V, the material structure still keeps stable and can develop higher gram capacity; the anode material is modified through artificial graphite and nature graphite, the actual gram capacity of the anode material approaches the theoretical gram capacity; and by adopting polyolefin-aromatic polyamide as a diaphragm material, the safety performance of the lithium-ion battery is effectively improved.
Description
Technical field
The invention belongs to technical field of lithium ion.
Background technology
Cobalt acid lithium (LiCoO
2) material adopted by vast lithium ion battery factory because of advantages such as its gram volume height, compacted density is big, voltage platform is high, good cycle always.The positive electrode that is used for the lithium ion battery of emerging electronic equipments such as smart mobile phone, net book at present mostly is cobalt acid lithium.
Traditional lithium ion cell charging upper voltage limit all is 4.2V, and this standard is LiCoO
2Battery charge to positive electrode macro molecules amount is Li
xCoO
2Middle x is the potential difference of 0.5 o'clock battery plus-negative plate.The reaction equation of charging process is as follows:
When the charging upper voltage limit of cobalt acid lithium battery during greater than 4.2V, Li
xCoO
2In x value will be less than 0.5, and a large amount of studies have shown that will cause LixCoO at this moment
2Take place to decompose and emit oxygen, cause battery performance to worsen, even explosive combustion.This threshold voltage has also limited the charging voltage of lithium ion battery, makes lithium ion battery that more high-octane performance can not be arranged.Therefore, seeking more, the electrode material of high-energy-density has just become inevitable.
In addition, traditional lithium ion battery separator material is the TPO macromolecular material.At present security performance do best for the TPO diaphragm material be PP-PE-PP (PP: propene carbonate, PE: 3-layer composite material ethylene carbonate).But its closed pore temperature is about 130 ℃, and broken film temperature is about 150 ℃, and the warm journey scope of closed pore-rupture of membranes is too small, and this will cause battery when thermal runaway, and barrier film will melt rapidly, both positive and negative polarity direct short-circuit, battery explosion, on fire.Therefore, the warm journey scope of the closed pore-rupture of membranes of prolongation barrier film is the key point that solves the lithium ion battery security energy.
Summary of the invention
The present invention seeks to break off relations the defective of prior art, a kind of high-energy-density safety-type lithium ion battery is provided.Above-mentioned purpose is realized by following technical scheme:
A kind of high-energy-density safety-type lithium ion battery comprises positive plate, negative plate, barrier film and electrolyte; It is characterized in that: the consisting of of positive plate slurry, by mass ratio: LiNi
xMn
yCo
1-x-yO
2: oxygen absorbent: carbon black: PVDF=92-96%: 0.1-3%: 1-3.5%: 2-3.5%, wherein 1≤x≤9,9 〉=y 〉=1; The slurry of negative plate consists of, by mass ratio: graphite: carbon black: CMC: SBR=91-95%: 1-3.5%: 1.2-2.5%: 1-3%; The barrier film of battery is that polyolefin porous membrane and aromatic polyamide fibre hot pressing are composited; The solvent of described electrolyte contains one or more in propene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, phosphoric acid methyl ethyl ester, dimethoxy-ethane, diethoxyethane, the ethylmethane sulfonate; The electrolyte of described electrolyte contains LiPF
6, LiBOB, LiBF
4And LiAsF
6In one or more; Additive is one or more in ethylene sulfite, vinylene carbonate, vinyl ethylene carbonate, vinyl ethylene sulfite, the trimethyl phosphate.
Described oxygen absorbent comprises: all organic substances that 1, contain two keys, carbonyl isoreactivity group on main chain or the side chain; 2 or contain all organic substances of active methylene group at main chain; 3 or all metals or metal oxide with reducing power.
Described positive plate surface is coated with SiO
2-PVDF laminated film.
A kind of preparation method of above-mentioned high-energy-density safety-type lithium ion battery is characterized in that, comprising:
The making of positive plate: at first, with LiNi
xMn
yCo
1-x-yO
2, oxygen absorbent, carbon black and PVDF mixture slurrying; Then, slurry is coated on the pole piece matrix, again drying, rolling and cut;
The making of negative plate: with the mixture slurrying of graphite, carbon black, CMC, SBR, control slurry viscosity 2500-4000mPa/s, through coating, oven dry, rolling, cut, work step such as spot welding makes negative plate;
The making of barrier film: be composited by polyolefin porous membrane and aromatic polyamide fibre hot pressing; And
The assembling of battery.
Described polyolefin porous membrane material comprises polyethylene hydrocarbon, polypropylene/olefin, and aromatic polyamide fibre comprises Fanglun 1414, Fanglun 1313 and poly fiber.
Above-mentioned preparation method also is included in the positive plate surface and is coated with SiO
2The step of-PVDF composite glue solution.
Wherein, described SiO
2-PVDF composite glue solution is made by following steps: the PVDF of 10wt% is dissolved among the PVDF, adds the SiO of 5wt% then
2In above-mentioned solution, be stirred to SiO
2Disperse fully.
Above-mentioned preparation method also comprises the burin-in process step, and its aging technique is: after the battery forming and capacity dividing is finished, battery is full of electricity, puts into the aging 0.5-6h of 45-80 ℃ of baking box.
Described aging technique is: electric core is full of electricity, puts into 60 ℃ the aging 1h of baking box.
Lithium ion battery provided by the invention, anodal pure ternary material has been concentrated LiCoO owing to good " conjugation " between nickel, cobalt and manganese element
2, LiMnO
2And LiNiO
2Advantage, have characteristics such as electrochemistry capacitance height, good cycle and cost are low, when charging upper voltage limit during greater than 4.3-4.5V, it is stable that material structure still keeps, and can give play to higher gram volume (reaching about 170mAh/g); Negative pole is by carrying out modification to Delanium and native graphite, and its actual gram volume near theoretical gram volume, reaches about 360mAh/g.In addition, lithium ion battery of the present invention is diaphragm material at the characteristics of ternary material and graphite material by adopting polyolefin-aromatic polyamide, has improved the security performance of lithium ion battery effectively.
Description of drawings
The lithium ion battery Performance Detection schematic diagram that Fig. 1 provides for embodiment.
Embodiment
The lithium ion battery that present embodiment provides comprises positive plate, negative plate, barrier film and electrolyte.Wherein, the active material of anode pole piece is nickel, cobalt, manganese ternary material, and is added with oxygen absorbent in the anode sizing agent; The positive plate surface scribbles one deck ceramic material (PVDF composite membrane).The barrier film of battery adopts the composite membrane of polyalkene diaphragm and aromatic polyamide.
The slurry of positive plate consists of active material: oxygen absorbent: carbon black: PVDF=92-96%: 0.1-3%: 1-3.5%: 2-3.5% (mass ratio).The molecular formula of described positive active material is LiNi
xMn
yCo
1-x-yO
2, 1≤x≤9,9 〉=y 〉=1.Described oxygen absorbent comprises: all organic substances that 1, contain two keys, carbonyl isoreactivity group on main chain or the side chain; 2 or contain all organic substances of active methylene group at main chain, as polybutadiene, polyisoprene, olefin copolymer, alkyne polymer, nylon 6, poly-m-phenylene adipamide (MXD6), (ethylene/vinyl alcohol) copolymer (E/VAL) etc.; 3 or all metals or metal oxide with reducing power, as iron, aluminium, zinc, ferrous oxide etc.
Anode pole piece can be coated with one deck micron order ceramic material-PVDF film on its surface, this film is made by following method: PVDF is dissolved in the PVDF-NMP solution that makes 1-20% in the nmp solution, micron order ceramic powders with 5-20% is dispersed in the above-mentioned solution then, be applied to the anode pole piece surface by the method for brushing, NMP is removed in 80-120 ℃ of baking.Described micron order ceramic material comprises SiO
2And Al
2O
3, particle diameter is at the 0.5-200 micron.
The slurry of the slurry negative plate of described negative plate consists of, by mass ratio: graphite: carbon black: CMC: SBR=91-95%: 1-3.5%: 1.2-2.5%: 1-3%.Graphite can be Delanium, modified natural graphite or above both admixed graphite; Cathode conductive agent is SUPER or KS6, or both use with any mixed.
Described electrolyte solvent is that usefulness contains one or more in propene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), phosphoric acid methyl ethyl ester (EMC), dimethoxy-ethane (DEE), diethoxyethane (DME), the ethylmethane sulfonate (EMS) etc.; Electrolyte is for containing LiPF
6, LiBOB, LiBF
4And LiAsF
6In one or more; Additive is one or more in ethylene sulfite (ES) vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), the trimethyl phosphate (DMMP) etc.
Described battery isolating film is by polyalkene diaphragm (individual layer PP, PE or multilayer PP-PE-PP film) and aromatic polyamide (as Fanglun 1414, Fanglun 1313 or poly fiber) compound composition.
The preparation technology of above-mentioned lithium ion battery is as follows:
1. positive plate is made: at first, press LiNi
1/3Mn
1/3Co
1/3O
2: oxygen absorbent: carbon black: PVDF=92: 2: 3.5: 2.5 ratio slurrying; Then, slurry is coated on the thick aluminium foil of 15 μ m, after the pole piece drying, is coated with the SiO of the about 5 μ m of a layer thickness equably on its surface
2-PVDF composite glue solution; At last, then gained solution evenly is applied to the positive plate surface.Pole piece drying, rolling etc., making surface recombination has SiO
2The compound pole piece of the ternary material of-PVDF.
Above-mentioned SiO
2-PVDF composite glue solution is made by following steps: the PVDF of 10wt% is dissolved among the PVDF, adds the SiO of 5wt% then
2In above-mentioned solution, be stirred to SiO
2Disperse fully.
2. negative plate is made: by graphite: carbon black: CMC: SBR=95: 1: 1.5: 2.5 ratio makes cathode size, controls slurry viscosity 2500-4000mPa/s, equally through coating, oven dry, rolling, cut, work step such as spot welding makes negative plate.
3. barrier film is made: barrier film is selected polypropylene-Fanglun 1313 composite diaphragm of 25 μ m for use.
4. battery is made: through reels, seal, fluid injection, change into, work steps such as shaping, partial volume make, battery manufacturing process belongs to the existing technology of knowing, herein detailed description no longer one by one.
5. burin-in process: after battery completes electric core is full of electricity, puts into 60 ℃ the aging 1h of baking box.Described aging technique is full of electricity for after the battery forming and capacity dividing finishes with battery, puts into the aging 0.5-6h of 45-80 ℃ of baking box.
The beneficial effect of the lithium ion battery that present embodiment provides is as follows:
1. battery 3C/20V overcharges, and battery is not on fire, does not explode, and security performance is better.
2. accompanying drawing 1 is the discharge curve of battery at the high charge upper voltage limit of difference.With 4.3V and 4.4V is the charging upper voltage limit, and battery capacity has promoted 7.5% and 14% when with 4.2V being the charging upper voltage limit respectively, has as seen improved the energy density of electrokinetic cell greatly.
3. added oxygen absorbent in anode pole piece, this oxidant can absorb battery because of a large amount of oxygen that thermal runaway produces, and avoids battery explosion on fire.
4. be coated with last layer ceramic material-PVDF film on the positive electrode surface of battery, when battery short circuit or acupuncture, extruding, avoid battery plus-negative plate directly to contact, further improved the security performance of battery.
5. adopt polyolefin-aromatic polyamide MULTILAYER COMPOSITE barrier film, because the fusing point of aromatic polyamide is up to 400 ℃, expand the warm journey scope (130-400 ℃) of barrier film from the closed pore to the rupture of membranes greatly, greatly dwindled battery causes battery explosion owing to thermal runaway danger.
6. battery is worn out through special aging flow process, make negative pole form fine and close SEI film, significantly improve the overcharging resisting performance of battery.
Claims (9)
1. a high-energy-density safety-type lithium ion battery comprises positive plate, negative plate, barrier film and electrolyte; It is characterized in that: the consisting of of positive plate slurry, by mass ratio: LiNi
xMn
yCo
1-x-yO
2: oxygen absorbent: carbon black: PVDF=92-96%: 0.1-3%: 1-3.5%: 2-3.5%, wherein 1≤x≤9,9 〉=y 〉=1; The slurry of negative plate consists of, by mass ratio: graphite: carbon black: CMC: SBR=91-95%: 1-3.5%: 1.2-2.5%: 1-3%; The barrier film of battery is that polyolefin porous membrane and aromatic polyamide fibre hot pressing are composited; The solvent of described electrolyte contains one or more in propene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, phosphoric acid methyl ethyl ester, dimethoxy-ethane, diethoxyethane, the ethylmethane sulfonate; The electrolyte of described electrolyte contains LiPF
6, LiBOB, LiBF
4And LiAsF
6In one or more; Additive is one or more in ethylene sulfite, vinylene carbonate, vinyl ethylene carbonate, vinyl ethylene sulfite, the trimethyl phosphate.
2. high-energy-density safety-type lithium ion battery according to claim 1, it is characterized in that: described oxygen absorbent comprises: all organic substances that 1, contain two keys, carbonyl isoreactivity group on main chain or the side chain; 2 or contain all organic substances of active methylene group at main chain; 3 or all metals or metal oxide with reducing power.
3. high-energy-density safety-type lithium ion battery according to claim 1 and 2 is characterized in that: described positive plate surface is coated with SiO
2-PVDF laminated film.
4. a method for preparing the described high-energy-density safety-type of claim 1 lithium ion battery is characterized in that, comprising:
The making of positive plate: at first, with LiNi
xMn
yCo
1-x-yO
2, oxygen absorbent, carbon black and PVDF mixture slurrying; Then, slurry is coated on the pole piece matrix, again drying, rolling and cut;
The making of negative plate: with the mixture slurrying of graphite, carbon black, CMC, SBR, control slurry viscosity 2500-4000mPa/s, through coating, oven dry, rolling, cut, work step such as spot welding makes negative plate;
The making of barrier film: be composited by polyolefin porous membrane and aromatic polyamide fibre hot pressing; And
The assembling of battery.
5. preparation method according to claim 4, it is characterized in that, described polyolefin porous membrane material comprises polyethylene hydrocarbon, polypropylene/olefin, and aromatic polyamide fibre comprises Fanglun 1414, Fanglun 1313 and poly fiber.
6. preparation method according to claim 4 is characterized in that, also is included in the positive plate surface and is coated with SiO
2The step of-PVDF composite glue solution.
7. preparation method according to claim 6 is characterized in that, described SiO
2-PVDF composite glue solution is made by following steps: the PVDF of 10wt% is dissolved among the PVDF, adds the SiO of 5wt% then
2In above-mentioned solution, be stirred to SiO
2Disperse fully.
8. preparation method according to claim 4 is characterized in that, also comprises the burin-in process step, and its aging technique is: after the battery forming and capacity dividing is finished, battery is full of electricity, puts into the aging 0.5-6h of 45-80 ℃ of baking box.
9. preparation method according to claim 8 is characterized in that, described aging technique is: electric core is full of electricity, puts into 60 ℃ the aging 1h of baking box.
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| CN2011102178679A CN102290597A (en) | 2011-08-01 | 2011-08-01 | Safe-type high-energy density lithium-ion battery |
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|---|---|---|---|
| CN2011102178679A CN102290597A (en) | 2011-08-01 | 2011-08-01 | Safe-type high-energy density lithium-ion battery |
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ID=45336815
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103606700A (en) * | 2013-11-15 | 2014-02-26 | 江苏天鹏电源有限公司 | Lithium ion battery with good charge and discharge performance |
| CN103985905A (en) * | 2014-05-30 | 2014-08-13 | 厦门大学 | An electrolyte with propylene carbonate as the main solvent |
| WO2015070706A1 (en) * | 2013-11-12 | 2015-05-21 | 江苏华东锂电技术研究院有限公司 | Electrode slurry, negative electrode, and lithium ion battery using the same |
| CN105849944A (en) * | 2013-12-26 | 2016-08-10 | 三洋电机株式会社 | Negative electrode for non-aqueous electrolyte secondary cell |
| CN107871891A (en) * | 2017-11-03 | 2018-04-03 | 欣旺达电子股份有限公司 | Optimize the method for lithium battery core performance |
| CN111477820A (en) * | 2020-05-16 | 2020-07-31 | 深圳市劢全新材料科技有限责任公司 | Aromatic polyester L CP composite diaphragm and lithium battery comprising same |
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| WO2015070706A1 (en) * | 2013-11-12 | 2015-05-21 | 江苏华东锂电技术研究院有限公司 | Electrode slurry, negative electrode, and lithium ion battery using the same |
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| CN107871891B (en) * | 2017-11-03 | 2019-10-25 | 欣旺达电子股份有限公司 | Optimize the method for lithium battery core performance |
| CN111477820A (en) * | 2020-05-16 | 2020-07-31 | 深圳市劢全新材料科技有限责任公司 | Aromatic polyester L CP composite diaphragm and lithium battery comprising same |
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Application publication date: 20111221 |