CN101651233A - Lithium ion secondary battery and preparation method thereof - Google Patents
Lithium ion secondary battery and preparation method thereof Download PDFInfo
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- CN101651233A CN101651233A CN200810145736A CN200810145736A CN101651233A CN 101651233 A CN101651233 A CN 101651233A CN 200810145736 A CN200810145736 A CN 200810145736A CN 200810145736 A CN200810145736 A CN 200810145736A CN 101651233 A CN101651233 A CN 101651233A
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- lithium rechargeable
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 50
- 239000006258 conductive agent Substances 0.000 claims abstract description 30
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 239000004642 Polyimide Substances 0.000 claims abstract description 20
- 229920001721 polyimide Polymers 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 239000007774 positive electrode material Substances 0.000 claims description 28
- 230000004888 barrier function Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 20
- 229920000767 polyaniline Polymers 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001197 polyacetylene Polymers 0.000 claims description 6
- 229920000128 polypyrrole Polymers 0.000 claims description 6
- 229920000123 polythiophene Polymers 0.000 claims description 6
- 150000002240 furans Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000013543 active substance Substances 0.000 abstract 1
- 229920000775 emeraldine polymer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- -1 LiVPO 4F Inorganic materials 0.000 description 8
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 159000000002 lithium salts Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
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- 239000011889 copper foil Substances 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
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- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920000015 polydiacetylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- ZTWBEOCMVOSCSU-UHFFFAOYSA-N lithium;oxotitanium Chemical compound [Li].[Ti]=O ZTWBEOCMVOSCSU-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
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- 150000008053 sultones Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium ion secondary battery. The lithium ion battery comprises a battery shell, a pole core and an electrolyte, wherein the pole core and the electrolyte are accommodated inthe battery shell; the pole core comprises a positive pole, a negative pole and a diaphragm positioned between the positive pole and the negative pole; the positive pole comprises a current collectorand positive materials; the positive materials comprise positive active substances, a conductive agent and a binder; the binder is provided with conductive performance; and the diaphragm is a porouspolyimide film. The invention also provides a preparation method for the lithium ion secondary battery. Due to the adoption of a conductive polymer serving as the positive binder and polyimide servingas the battery diaphragm, the lithium ion secondary battery provided by the invention significantly increases the capacity and the cycle performance of the battery, and significantly improves the high-rate charge and discharge performance.
Description
Technical field
The present invention relates to a kind of lithium rechargeable battery and preparation method thereof.
Background technology
In recent years, the high speed development of electronic technology makes the electronic equipment can miniaturization and lightweight, thereby increasing portable electric appts occurred.Lithium rechargeable battery is with its discharge voltage height, energy density height and recycle the first-selected energy that long advantage of life-span becomes these portable electric appts.
The capacity of lithium rechargeable battery and cycle performance are the lithium rechargeable battery main performance index, and it is bigger that capacitance and cycle performance are influenced by the resistance of battery.Lithium rechargeable battery mainly is made up of positive pole, negative pole, barrier film and electrolyte.Positive pole comprises collector and the positive electrode that loads on the collector, and described positive electrode contains positive active material, conductive agent and binding agent.Negative pole comprises collector and the negative material that loads on the collector, and described negative material contains negative electrode active material, conductive agent and binding agent.The resistance of battery mainly comprises the resistance of positive and negative electrode, the resistance of electrolyte, the resistance of barrier film.The method of traditional reduction resistance comprises that kind by the material of choice set fluid and active material and conductive agent is to reduce the resistance of positive pole and/or negative pole.
In battery, anodal performance is very big to the performance impact of battery, and the performance of traditional positive pole is mainly determined by the performance of positive active material and conductive agent, and traditional binding agent only provides the cohesive force between positive electrode active materials, conductive agent and the collector.Discover when used binding agent has electric conductivity, can improve electronics and lithium ion and in battery, move fast, thus the charge/discharge capacity of raising battery.
Electric conductive polymer or conducting polymer are meant can be by the general designation of insulator to the polymer that contains the pi-electron conjugated structure of conductor or semiconductor transformation behind chemistry or electrochemical doping.The polyacetylene (PA) that mixes from iodine is found so far, and found successively polyaniline (PANI), polypyrrole (PPY), polythiophene (PT), polydiacetylene (PDA) and polyphenylacetylene (PPA) can be used as the matrix of electric conductive polymer.The polyaniline that will have electric conductivity uses in the lithium ion battery as binding agent, can reduce the internal resistance of battery, improves charge/discharge capacity.For example, CN 1809937A discloses a kind of electrode activity composition that is used for electrochemical cell, and said composition comprises active electrode material and electric conductive polymer.But the capacitance that adopts this method to increase is limited, can not satisfy the demand of current electronic equipment to high capacity cell.
Summary of the invention
The objective of the invention is provides a kind of capacitance higher lithium rechargeable battery in order to overcome the lower defective of capacity of the lithium rechargeable battery that prior art provides.
The invention provides a kind of lithium rechargeable battery, this lithium rechargeable battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, positive pole comprises collector and positive electrode, and described positive electrode contains positive active material, conductive agent and binding agent, wherein, described binding agent is the binding agent with electric conductivity, and described barrier film is the polyimides porous membrane.
The invention provides a kind of preparation method of lithium rechargeable battery, this method comprises positive pole, barrier film and the negative pole formation pole piece of reeling successively, pole piece is inserted in the battery case, add electrolyte, then sealing, wherein, the preparation method of described positive pole comprises positive electrode is loaded on the collector that described positive electrode contains positive active material, conductive agent and binding agent, wherein, described binding agent is the binding agent with electric conductivity, and described barrier film is the polyimides porous membrane.
Adopt electric conductive polymer can reduce the internal resistance of cell, thereby can improve the capacity of battery as positive binder; When adopting polyimides, because it has the big and porosity advantages of higher in aperture, can improve the migration velocity of lithium ion in electrolyte, thereby improve the capacity and the cycle performance of battery as lithium ion battery separator.
The present inventor is surprised to find that when adopting electric conductive polymer as positive binder and when adopting polyimides as battery diaphragm, synergy has appearred, promptly improve the capacity and the cycle performance of battery significantly, can also obviously improve high-rate charge-discharge capability in addition.0.2C discharge capacity as the battery of embodiment 1 preparation is 830 MAHs, and the 0.2C discharge capacity of the batteries of Comparative Examples 1,2 and 3 preparations is respectively 795 MAHs, 790 MAHs and 780 MAHs; The cycle-index of the battery of embodiment 1 preparation is 500, and the cycle-index of the batteries of Comparative Examples 1,2 and 3 preparations is respectively 437,431 and 420, therefore, is used in combination conductive adhesive and the pi barrier film shows strong cooperative effect.
Embodiment
The invention provides a kind of lithium rechargeable battery, this lithium ion battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, positive pole comprises collector and positive electrode, and described positive electrode contains positive active material, conductive agent and binding agent, wherein, described binding agent is the binding agent with electric conductivity, and described barrier film is polyimides porous membrane (PI).
In lithium rechargeable battery of the present invention, the porosity of described polyimides porous membrane can be for being 40-60%; Its average pore diameter can be the 80-100 nanometer.Its thickness can be the 16-25 micron, is preferably the 18-22 micron.
In lithium rechargeable battery of the present invention, described binding agent with electric conductivity can be electric conductive polymer, described electric conductive polymer can be employed electric conductive polymer in the prior art, be preferably the electric conductive polymer that conductance is every centimetre of 1-30 Siemens (S/cm), most preferably be every centimetre of 5-25 Siemens.
Among the present invention, described electric conductive polymer can be one or more the cationization product in polyaniline, polythiophene, polypyrrole, polyacetylene, polyphenylacetylene, the poly-furans.The degree of cationization depends on needed conductance.Described cationization product comprises protonated product or metal cation product.A kind of preferred embodiment in, described electric conductive polymer is the protonated product of polyaniline.Polyaniline can exist with several frequently seen form, comprise that it goes back the emeraldine base (emeraldine) of the emeraldine base that fades (leucoemeradine) of original shape, partial oxidation and the full nigrosine (pernigraniline) of complete oxidation, their general formula is as follows:
Emeraldine base fades
Emeraldine base
Full nigrosine
Normally used polyaniline exists with the form of their mixture, and its general formula is:
When 0≤y≤1, polyaniline is called poly-p-phenylenediamine (PPD) imines, wherein the oxidation state of this polymer with y value reduce and constantly increase.Be the poly-p-phenylenediamine (PPD) imines that reduces fully when y=0, be also referred to as the emeraldine base that fades; When 0.35≤y≤0.65, be called emeraldine base.Therefore, " emeraldine base fades ", " emeraldine base ", " full nigrosine " are meant the polyaniline of different oxidation state.Each oxidation state can exist with its alkali, form protonated or cationization.Term " protonated " is meant by polymer is contacted with Bronsted acid, thereby adds hydrogen ion in this polymer.Described Bronsted acid can be inorganic acid and organic acid.Described inorganic acid is one or more in hydrochloric acid, sulfuric acid, the nitric acid; Described organic acid is one or more in methanesulfonic acid, toluenesulfonic acid, DBSA and the camphorsulfonic acid.The method of contact has been conventionally known to one of skill in the art with the condition that contacts, and the present invention does not repeat them here.
The emeraldine base that fades is an electric insulation, and protonated emeraldine base has high conductivity.Protonated emeraldine base can make its protonated acquisition by using Bronsted acid, example hydrochloric acid to contact with emeraldine base; Also can be by electrochemical oxidation in the electrolyte of proper pH value protonated the fade emeraldine base or the protonated full nigrosine acquisition of reducing.
Above-mentioned electric conductive polymer can obtain by variety of way, for example, can be commercially available, also can prepare by means commonly known in the art.
In lithium rechargeable battery of the present invention, the content of described binding agent, positive active material and conductive agent is customary amount; Being preferably, is benchmark with the total weight of positive active material, conductive agent and binding agent, and the content of described binding agent is 0.5-10 weight %, most preferably is 0.5-2 weight %; The content of described positive active material is 85-90 weight %; The content of described conductive agent is 0.5-5 weight %.
The present invention has no particular limits positive active material, and is the same with prior art.Described positive active material can adopt all positive active materials that can be purchased, as LiFePO
4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F, LiFeO
2Perhaps ternary system Li
1+ aL
1-b-cM
bN
cO
2, wherein-0.1≤a≤0.2,0≤b≤1,0≤c≤1,0≤b+c≤1.0, L, M, N be in Co, Mn, Ni, Al, Mg, Ga and the 3d transiting group metal elements one or more.
Described conductive agent can adopt any conductive agent known in the field, for example can adopt in graphite, carbon fiber, carbon black, metal dust and the fiber one or more.
Anodal preparation method can adopt this area the whole bag of tricks commonly used, for example positive active material, binding agent and conductive agent are prepared into the positive electrode slurries with solvent, the addition of solvent is known in those skilled in the art, and the viscosity that can be coated with according to the slurry of the anodal slurries that will prepare and the requirement of operability are adjusted flexibly.Then prepared positive electrode slurries slurry is coated in dry compressing tablet on the positive electrode collector, cut-parts obtain positive pole again.The temperature of described drying can be 80-150 ℃, and can be 2-10 hour drying time.
The used solvent of described anodal slurries can be an all kinds of solvents of the prior art, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of solvent can be coated on the described conducting base described slurry and gets final product.In general, it is 40-90 weight % that the consumption of solvent makes the content of positive active material in the slurries, is preferably 50-85 weight %.
Described negative pole adopts this area negative pole in common knowledge, promptly contains negative current collector and the negative material that is coated on this negative current collector.Described collector can adopt the various collectors that are used for lithium ion secondary battery negative pole in the prior art, as Copper Foil.Anticathode material of the present invention has no particular limits, and is the same with prior art, and described negative electrode material layer generally includes negative electrode active material, binding agent and conductive agent.Described negative electrode active material can adopt all negative electrode active materials that can be purchased, as graphite and lithium titanium oxygen compound.Described conductive agent can be nickel powder and/or copper powder.Described binding agent can be the various binding agents that are used for lithium ion secondary battery negative pole in the prior art, as being in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) and the butadiene-styrene rubber (SBR) one or more.The preparation method of described negative pole is similar with anodal preparation method, is not described in detail in this.
In lithium rechargeable battery of the present invention, electrolyte is nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
The preparation method of lithium rechargeable battery provided by the invention is as well known to those skilled in the art, in general, this method comprises positive pole, the rich successively volume of negative pole and the barrier film between positive pole and negative pole forms pole piece, pole piece is inserted in the battery case, add electrolyte, sealing then, wherein, described positive pole comprises collector and the positive electrode that loads on the collector, described positive electrode contains positive active material, conductive agent and binding agent, wherein, described binding agent is the binding agent with electric conductivity, and described barrier film is the polyimides porous membrane.Wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is a conventional amount used.Wherein, in preferred embodiment, described polyimides porous membrane and electric conductive polymer are with above preferred polyimides porous membrane is identical with electric conductive polymer.In another preferred embodiment, total weight with positive active material, conductive agent and binding agent is a benchmark, the content of described binding agent is 0.5-10 weight %, and the content of described positive active material is 85-90 weight %, and the content of described conductive agent is 0.5-5 weight %.
Below be that example illustrates lithium rechargeable battery of the present invention with 053450 size battery.
Embodiment 1
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention.
Anodal: with positive active material LiCoO
2, conductive agent acetylene black as the electric conductive polymer (the cationization product of polyaniline, conductance are 10S/cm, EHSY company) of binding agent, is mixed well by weight 100: 5: 2 usefulness solvent NMP.Be two-sided dressing on 20 microns the aluminium foil at thickness, smear evenly.100 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 450cm (length) * 44cm (wide) * 0.12cm (thick), contains 7 gram positive active materials.
Negative pole:, in deionized water evenly mix at 100: 5: 3 according to weight ratio with Delanium, binding agent SBR and CMC.Be two-sided dressing on 12 microns the Copper Foil at thickness, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 480cm (length) * 45cm (wide) * 0.2cm (thick), and negative material weighs 3.4 grams.
Barrier film: adopt the polyimides porous membrane of 20 micron thickness, porosity is 40%, and average pore diameter is 90 nanometers.
With the lithium-ion electric core of an above-mentioned positive and negative plate and a square of membrane coil coiled and be received in the rectangular cell shell, inject 1 mol LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 1) electrolyte, the lithium ion battery 1 of 053450 type is made in sealing.
Embodiment 2
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention.
Anodal: with positive active material LiCoO
2, conductive agent acetylene black as the electric conductive polymer (conductance is 8S/cm for the cationization product of polythiophene, EHSY company) of binding agent, is mixed well by weight 100: 5: 0.5 usefulness NMP.Be two-sided dressing on 20 microns the aluminium foil at thickness, smear evenly.100 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 450cm * 44cm, and positive electrode weighs 7 grams.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopt the polyimides porous membrane of 25 micron thickness, porosity is 60%, and average pore diameter is 80 nanometers.
Method assembled battery 2 according to embodiment 1.
Embodiment 3
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention.
In the present embodiment, positive pole: adopt positive active material LiCoO
2, conductive agent acetylene black as the electric conductive polymer (conductance is 20S/cm for the cationization product of polypyrrole, EHSY company) of binding agent, was evenly mixed in the NMP the inside by weight 100: 5: 5.Be two-sided dressing on 20 microns the aluminium foil at thickness, smear evenly.Dry in the baking of vacuum oven the inside, suppress afterwards.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopt the polyimides porous membrane of 16 micron thickness, porosity is 50%, and average pore diameter is 70 nanometers.
Method assembled battery 3 according to embodiment 1.
Embodiment 4
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention.
Anodal: as to adopt positive active material LiCoO
2, conductive agent acetylene black as the electric conductive polymer (conductance is 25S/cm for the cationization product of polyacetylene, EHSY company) of binding agent, was evenly mixed in the NMP the inside by weight 100: 5: 10.Be two-sided dressing on 20 microns the aluminium foil at thickness, smear evenly.Dry in the baking of vacuum oven the inside, suppress afterwards.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopt the polyimides porous membrane of 20 micron thickness, porosity is 40%, and average pore diameter is 90 nanometers.
Method assembled battery 4 according to embodiment 1.
Comparative Examples 1
This Comparative Examples is used to the lithium rechargeable battery that illustrates that prior art provides.
Anodal: prepare anodal method according to embodiment 1 and carry out, different is that binding agent adopts PVDF.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopt the barrier film identical with embodiment 1.
Method assembled battery C1 according to embodiment 1.
Comparative Examples 2
This Comparative Examples is used to the lithium rechargeable battery that illustrates that prior art provides.
Anodal: as to prepare anodal method according to embodiment 1 and carry out.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopt 20 microns polyethylene porous membrane, porosity is 40%, and average pore diameter is 100 nanometers.
Method assembled battery C2 according to embodiment 1.
Comparative Examples 3
This Comparative Examples is used to the lithium rechargeable battery that illustrates that prior art provides.
Anodal: as to prepare anodal method according to embodiment 1 and carry out, except that binding agent adopts PVDF.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.
Barrier film: adopting 20 microns polypropylene porous membrane porosity is 40%, and average pore diameter is 100 nanometers.
Method assembled battery C3 according to embodiment 1.
Battery performance test
1, the test of multiplying power discharging property
Under the room temperature, use the 1C current charges to 4.2V respectively on the battery of embodiment 1-4 and Comparative Examples 1-3 preparation, after voltage rose to 4.2 volts, with 4.2 volts of constant-potential charges, cut-off current was 0.05C, shelved 5 minutes; Then battery is lied prostrate with 0.2C current discharge to 3 respectively, obtain the capacity that battery lies prostrate with 0.2C current discharge to 3 at normal temperatures; Repeat above-mentioned charge step then, and once more respectively with battery with the 0.5C current discharge, obtain battery at normal temperatures with the capacitance of 0.5C current discharge to 3 volt; Repeat above-mentioned charge step then, and once more respectively with battery with the 1C current discharge, obtain battery at normal temperatures with the capacitance of 1C current discharge to 3 volt; Repeat above-mentioned charge step then, and once more respectively with battery with the 2C current discharge, obtain battery at normal temperatures with the capacitance of 2C current discharge to 3 volt; Repeat above-mentioned charge step then, and once more respectively with battery with the 3C current discharge, obtain battery at normal temperatures with the capacitance of 3C current discharge to 3 volt; And then repeat above-mentioned charge step, and once more respectively with battery with the 5C current discharge, obtain battery at normal temperatures with the results are shown in the table 1 that the capacitance of 5C current discharge to 3 volt records.
2, the mensuration of cycle performance
Under the room temperature, the battery that embodiment 1-4 and Comparative Examples 1-3 are made lies prostrate with 1C current charges to 4.2 respectively, after voltage rises to 4.2 volts, with 4.2 volts of constant-potential charges, cut-off current is 0.05C, shelved 5 minutes, and then battery was lied prostrate with 1C current discharge to 3 respectively, obtain the capacity of battery normal temperature 1C current discharge to 3 volt; Discharge and recharge step more than the repetition and stop test up to battery capacity for 80% of the capacitance measured for the first time, what record the results are shown in the table 1.
3, the mensuration of the internal resistance of cell
The battery that embodiment 1-4 and Comparative Examples 1-3 are made is under 20 ± 5 ℃ the condition, with 0.1C (120 milliamperes) charging 16 hours in ambient temperature, after charging finishes, shelved 1 hour, the internal resistance instrument test internal resistance of producing then with Guangzhou Lan Qi company, what record the results are shown in the table 1.
Table 1
As can be seen from Table 1, the capacitance of the battery of embodiment 1-4 preparation and cycle performance are significantly higher than the capacitance and the cycle performance of the battery of Comparative Examples 1-3 preparation; And internal resistance significantly is lower than the internal resistance of the battery of Comparative Examples 1-3 preparation.Therefore, be used in combination conductive adhesive and the pi barrier film shows strong cooperative effect.
Claims (12)
1, a kind of lithium rechargeable battery, this lithium ion battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, positive pole comprises collector and the positive electrode that loads on the collector, described positive electrode contains positive active material, conductive agent and binding agent, it is characterized in that, described binding agent is the binding agent with electric conductivity, and described barrier film is the polyimides porous membrane.
2, lithium rechargeable battery according to claim 1, wherein, the porosity of described polyimides porous membrane is 40-60%, average pore diameter is the 80-100 nanometer.
3, lithium rechargeable battery according to claim 1 and 2, wherein, the thickness of described polyimides porous membrane is the 16-25 micron.
4, lithium rechargeable battery according to claim 1, wherein, described binding agent with electric conductivity is an electric conductive polymer, the conductance of described electric conductive polymer is every centimetre of a 1-30 Siemens.
5, lithium rechargeable battery according to claim 4, wherein, described electric conductive polymer is one or more protonated product or the cationization product in polyaniline, polythiophene, polypyrrole, polyacetylene, polyphenylacetylene, the poly-furans.
6, lithium rechargeable battery according to claim 1, wherein, total weight with positive active material, conductive agent and binding agent is a benchmark, the content of described binding agent is 0.5-10 weight %, the content of described positive active material is 85-90 weight %, and the content of described conductive agent is 0.5-5 weight %.
7, the preparation method of the described lithium rechargeable battery of a kind of claim 1, this method comprises positive pole, barrier film and the negative pole formation pole piece of reeling successively, pole piece is inserted in the battery case, add electrolyte, sealing then, wherein, the preparation method of described positive pole comprises positive electrode is loaded on the collector, described positive electrode contains positive active material, conductive agent and binding agent, it is characterized in that, described binding agent is the binding agent with electric conductivity, and described barrier film is the polyimides porous membrane.
8, the preparation method of lithium rechargeable battery according to claim 7, wherein, the porosity of described polyimides porous membrane is 40-60%, average pore diameter is the 80-100 nanometer.
9, according to the preparation method of claim 7 or 8 described lithium rechargeable batteries, wherein, the thickness of described polyimides porous membrane is the 16-25 micron.
10, the preparation method of lithium rechargeable battery according to claim 7, wherein, described binding agent with electric conductivity is an electric conductive polymer, the conductance of described electric conductive polymer is every centimetre of a 1-30 Siemens.
11, the preparation method of lithium rechargeable battery according to claim 10, wherein, described electric conductive polymer is one or more the cationization product in polyaniline, polythiophene, polypyrrole, polyacetylene, polyphenylacetylene, the poly-furans.
12, the preparation method of lithium rechargeable battery according to claim 8, wherein, total weight with positive active material, conductive agent and binding agent is a benchmark, the content of described binding agent is 0.5-10 weight %, the content of described positive active material is 85-90 weight %, and the content of described conductive agent is 0.5-5 weight %.
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| CN200810145736A CN101651233A (en) | 2008-08-14 | 2008-08-14 | Lithium ion secondary battery and preparation method thereof |
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| CN102487141B (en) * | 2010-12-02 | 2014-08-13 | 比亚迪股份有限公司 | Cathode material of lithium ion battery and battery |
| CN102487141A (en) * | 2010-12-02 | 2012-06-06 | 比亚迪股份有限公司 | Cathode material of lithium ion battery and battery |
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| US10978693B2 (en) | 2016-06-15 | 2021-04-13 | Ningbo Institute Of Materials Technology And Engineering, Chinese Academy Of Sciences | Battery paste, battery electrode plate, and preparation method therefor |
| CN111640921A (en) * | 2020-05-22 | 2020-09-08 | 大连海事大学 | Preparation method of vanadium compound electrode material and application of vanadium compound electrode material in water-based zinc ion battery |
| CN116154178A (en) * | 2023-04-23 | 2023-05-23 | 宁德时代新能源科技股份有限公司 | Positive electrode plate, battery cell, battery and electricity utilization device |
| CN116154178B (en) * | 2023-04-23 | 2023-09-01 | 宁德时代新能源科技股份有限公司 | Positive electrode plate, battery cell, battery and electricity utilization device |
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