CN103904299B - Lithium rechargeable battery and cathode pole piece thereof - Google Patents

Lithium rechargeable battery and cathode pole piece thereof Download PDF

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Publication number
CN103904299B
CN103904299B CN201410110152.7A CN201410110152A CN103904299B CN 103904299 B CN103904299 B CN 103904299B CN 201410110152 A CN201410110152 A CN 201410110152A CN 103904299 B CN103904299 B CN 103904299B
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pole piece
rechargeable battery
lithium rechargeable
monomer
cathode pole
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CN103904299A (en
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洪响
钟开富
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention provides a kind of lithium rechargeable battery and cathode pole piece thereof.The cathode pole piece of described lithium rechargeable battery comprises: negative current collector; And cathode membrane, to be arranged on negative current collector and to comprise negative active core-shell material, binding agent.Described binding agent comprises the conducting polymer by the monomer crosslinked copolymerization with crosslinkable groups, and described monomer comprises the monomer with molecular formula 1 and molecular formula 2 structure.Lithium rechargeable battery of the present invention comprises: anode pole piece, comprises plus plate current-collecting body, is arranged on plus plate current-collecting body and comprises the positive pole diaphragm of positive electrode active materials; Cathode pole piece; Barrier film, is interval between anode pole piece and cathode pole piece; And electrolyte, comprise lithium salts and non-aqueous organic solvent.Lithium rechargeable battery of the present invention has good cycle performance and high-rate charge-discharge capability.

Description

Lithium rechargeable battery and cathode pole piece thereof
Technical field
The present invention relates to field of batteries, particularly relate to a kind of lithium rechargeable battery and cathode pole piece thereof.
Background technology
Can use under high voltages due to lithium rechargeable battery and have higher energy density, it is used widely in portable type electronic product.But along with the development of electronic product pocketing and multifunction, the energy density of lithium rechargeable battery is had higher requirement.
As the capacity of the graphite-like material with carbon element of the negative active core-shell material of current most widely used lithium rechargeable battery close to its theoretical value (376mAh/g), but even if through improving, its energy density is also difficult to be further improved.The alloy material (capacity is up to 4200mAh/g) such as silicon and tin in this context with higher theoretical energy density attracts wide attention.But (about 400%) can be changed a lot at the volume of Lithium-ion embeding/the deviate from alloy material such as silicon and tin in process, and also progressively can be separated with conductive agent (conductive black etc.) in collector and cathode pole piece in lithium rechargeable battery charge and discharge cycles process, thus cause active material to lose efficacy and lithium ion secondary battery capacity sharp-decay.
For alleviating the capacity attenuation of the lithium rechargeable battery containing alloy type negative active core-shell material, solution uses the high molecular polymer with conductivity as a binding agent for alloy type negative active core-shell material, thus ensure alloy type negative active core-shell material after volumetric expansion (or contraction) still can and negative current collector between have good electrical conductivity.Chinese patent application CN101651233A discloses a kind of lithium rechargeable battery and preparation method thereof disclosed in the 17 days February in 2010, use the conducting polymer (polyaniline, poly-pyrrole are pressed against, Ju Sai Pin etc.) with linear chain structure as the binding agent of anode active material of lithium ion secondary battery, to improve the electronic conduction ability in anode pole piece, and significantly improve high-rate discharge ability and the cycle performance of lithium rechargeable battery.But due to the high polymer main chain of this type of conducting polymer only containing rigidity, the cementitiousness of anticathode active material is more weak, when being directly used in the cathode pole piece containing alloy type negative active core-shell material, need greatly to improve its consumption to ensure there is enough cementitiousness to suppress the change in volume of alloy type negative active core-shell material in charge and discharge process.Such one side can reduce the relative amount of negative active core-shell material in cathode pole piece, thus causes the reduction of lithium rechargeable battery integral energy density; On the other hand, because this kind of conducting polymer does not have lithium ion conduction performance, excessive use can hinder the conduction of lithium ion in pole piece thus cause serious polarization phenomena.On March 30th, 2011, the Chinese patent CN101867037B of Granted publication disclosed a kind of combination electrode material for high-power lithium ion secondary cell and preparation method thereof, wherein use the binding agent of mixture as lithium rechargeable battery of organic conductive polymer and non-conductive polymer, not only keep the cohesive force of the binding agent of conventional lithium ion secondary cell, and the electric conductivity of the pole piece of raising lithium rechargeable battery.But not there is lithium ion conduction performance due to these polymer itself, very limited to the improvement of performance of lithium-ion secondary battery.
Summary of the invention
In view of Problems existing in background technology, the object of the present invention is to provide a kind of lithium rechargeable battery and cathode pole piece thereof, it has good cycle performance and high-rate charge-discharge capability.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of cathode pole piece of lithium rechargeable battery, it comprises: negative current collector; And cathode membrane, to be arranged on negative current collector and to comprise negative active core-shell material, binding agent.Described binding agent comprises the conducting polymer by the monomer crosslinked copolymerization with crosslinkable groups, and described monomer comprises the monomer with molecular formula 1 and molecular formula 2 structure; In molecular formula 1 and molecular formula 2: the one that P is selected from hydrogen atom, has the alkyl of 1 ~ 12 carbon atom, has the alkoxyl of 1 ~ 12 carbon atom, has the cycloalkyloxy of 1 ~ 12 carbon atom, has the itrile group of 1 ~ 12 carbon atom, has the sulfonate group of 1 ~ 12 carbon atom and have in the carboxylic acid ester groups of 1 ~ 12 carbon atom; X is selected from S, NR 1, R 1the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom, there is the carboxylic acid ester groups of 1 ~ 12 carbon atom and have in the sulfonate group of 1 ~ 12 carbon atom; Y is selected from the one in-O-,-C (=O) O-,-C (=O) NH-,-NH-; Z is selected from O, NR 2, R 2the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom and have in the aromatic radical of 6 ~ 14 carbon atoms; B is selected from hydrogen atom, has one in the alkyl of 1 ~ 12 carbon atom; G is selected from hydrogen atom, reactive silicon group, alkylene, the ketone containing alkylene, the ether containing alkylene, the ester containing alkylene, the acid amides containing alkylene, alkyl containing halogen, hydroxyl or reactive silicon group and containing a kind of in the aromatic radical of halogen, alkylene, hydroxyl or reactive silicon group; It is hydrogen atom when B and G is different; N is the integer between 1 ~ 20.
In a second aspect of the present invention, the invention provides a kind of lithium rechargeable battery, it comprises: anode pole piece, comprises plus plate current-collecting body, is arranged on plus plate current-collecting body and comprises the positive pole diaphragm of positive electrode active materials; Cathode pole piece; Barrier film, is interval between anode pole piece and cathode pole piece; And electrolyte, comprise lithium salts and non-aqueous organic solvent.Wherein, described cathode pole piece is the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention.
Beneficial effect of the present invention is as follows:
1. relative to common conductive macromolecule, the binding agent of cathode pole piece of the present invention can form the good conductive polymer network of electric conductivity in pole piece manufacturing process, except effectively increasing except its short distance conductive capability, also by the crosslinked long-range conductive capability providing common conductive macromolecule to provide.
2. the binding agent of cathode pole piece of the present invention can substitute or Some substitute lithium rechargeable battery cathode pole piece in inorganic conductive agent, thus improve the energy density of lithium rechargeable battery.
3. the side chain of the binding agent of cathode pole piece of the present invention can contain polyethers or polyamine structure, makes it have good to lead lithium ion performance, greatly can improve the high rate performance of lithium rechargeable battery.
4. the binding agent of cathode pole piece of the present invention has crosslinkable groups, in the preparation process of cathode pole piece, improves its cementitiousness, and effectively prevents coming off of negative active core-shell material, thus improves the cycle performance of lithium rechargeable battery.
5. the binding agent preparation of cathode pole piece of the present invention is simple, is particularly suited for, in the lithium rechargeable battery for high-energy-density, having higher use value and application prospect.
Embodiment
The following detailed description of lithium rechargeable battery according to the present invention and cathode pole piece thereof and comparative example, embodiment and test result.
First the cathode pole piece of lithium rechargeable battery is according to a first aspect of the present invention described.
The cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, comprising: negative current collector; And cathode membrane, to be arranged on negative current collector and to comprise negative active core-shell material, binding agent.Described binding agent comprises the conducting polymer by the monomer crosslinked copolymerization with crosslinkable groups, and described monomer comprises the monomer with molecular formula 1 and molecular formula 2 structure; In molecular formula 1 and molecular formula 2: the one that P is selected from hydrogen atom, has the alkyl of 1 ~ 12 carbon atom, has the alkoxyl of 1 ~ 12 carbon atom, has the cycloalkyloxy of 1 ~ 12 carbon atom, has the itrile group of 1 ~ 12 carbon atom, has the sulfonate group of 1 ~ 12 carbon atom and have in the carboxylic acid ester groups of 1 ~ 12 carbon atom; X is selected from S, NR 1, R 1the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom, there is the carboxylic acid ester groups of 1 ~ 12 carbon atom and have in the sulfonate group of 1 ~ 12 carbon atom; Y is selected from the one in-O-,-C (=O) O-,-C (=O) NH-,-NH-; Z is selected from O, NR 2, R 2the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom and have in the aromatic radical of 6 ~ 14 carbon atoms; B is selected from hydrogen atom, has one in the alkyl of 1 ~ 12 carbon atom; G is selected from hydrogen atom, reactive silicon group, alkylene, the ketone containing alkylene, the ether containing alkylene, the ester containing alkylene, the acid amides containing alkylene, alkyl containing halogen, hydroxyl or reactive silicon group and containing a kind of in the aromatic radical of halogen, alkylene, hydroxyl or reactive silicon group; It is hydrogen atom when B and G is different; N is the integer between 1 ~ 20.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, in described conducting polymer: the mole percent that the monomer with molecular formula 1 structure accounts for monomer overall can be 10% ~ 99.9%; The mole percent that the monomer with molecular formula 2 structure accounts for monomer overall can be 0.1% ~ 90%.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described monomer also can comprise the monomer with molecular formula 3 structure.Because the conductive capability of conducting polymer is mainly provided by the high polymer main chain containing conjugation aromatic rings, what have the monomer of molecular formula 3 structure adds the structure and molecular weight that can regulate conducting polymer, thus controls the electric conductivity of conducting polymer.In molecular formula 3: the one that P is selected from hydrogen atom, has the alkyl of 1 ~ 12 carbon atom, has the alkoxyl of 1 ~ 12 carbon atom, has the cycloalkyloxy of 1 ~ 12 carbon atom, has the itrile group of 1 ~ 12 carbon atom, has the sulfonate group of 1 ~ 12 carbon atom and have in the carboxylic acid ester groups of 1 ~ 12 carbon atom; X is selected from S, NR 1, R 1the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom, there is the carboxylic acid ester groups of 1 ~ 12 carbon atom and have in the sulfonate group of 1 ~ 12 carbon atom.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described negative current collector can be selected from stainless steel, nickel, copper, titanium, carbon, electroconductive resin, the copper sheet being coated with nickel or titanium and the one be coated with in the stainless steel substrates of nickel or titanium.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described conducting polymer can account for 0.1% ~ 10% of described negative active core-shell material total weight, preferably can be 1% ~ 5%.Conducting polymer proportion is too low cannot provide good bond effect, and conducting polymer proportion is too high, can reduce the energy density of lithium rechargeable battery.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, in described conducting polymer: the mole percent that the monomer with molecular formula 1 structure accounts for monomer overall can be 10% ~ 80%; The mole percent that the monomer with molecular formula 2 structure accounts for monomer overall can be 0.1% ~ 30%; The mole percent that the monomer with molecular formula 3 structure accounts for monomer overall can be 0% ~ 70%.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described conducting polymer can be prepared from through electrochemically oxidative polymerization or chemical oxidising polymerisation by monomer, the weight average molecular weight of described conducting polymer can be 10000 ~ 2000000, preferably can be 50000 ~ 500000.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described electrochemically oxidative polymerization reaction can comprise step: by monomer and electrolyte dissolution obtained monomer solution in a solvent, monomer solution is placed in again by work electrode with to electrode, and electrochemically oxidative polymerization reaction is carried out under certain electric current, products therefrom, after solvent clean, obtains conducting polymer in working electrode surface.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described chemical oxidising polymerisation reaction can comprise step: monomer, solvent and oxidant are carried out chemical oxidising polymerisation in neutrality or sour environment, and the sediment be obtained by reacting obtains conducting polymer after solvent wash.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, electrochemically oxidative polymerization or chemical oxidising polymerisation are prepared in the process of conducting polymer, the solvent used of different phase can independently selected from be selected from deionized water, ethers, ester class, nitrile, amide-type, alcohols and halogenated alkane one or more.Described ethers can be selected from least one in ether, oxolane.Described ester class can be selected from least one in ethyl acetate, methyl formate, repefral.Described nitrile can be acetonitrile.Described amide-type can be selected from least one in 1-METHYLPYRROLIDONE, DMF.Described alcohols can be selected from least one in methyl alcohol, ethanol, isopropyl alcohol.Described halogenated alkane can be selected from least one in carrene, chloroform, dichloroethanes.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described electrolyte can comprise organic ammonium salt.Described organic ammonium salt can be selected from least one in tetraethyl ammonium tetrafluoroborate, TBuA hexafluorophosphate and TBuA tetrafluoroborate.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described oxidant can be selected from least one in inorganic oxidizer and organic oxidizing agent.Described inorganic oxidizer can be selected from least one in ferric trichloride, hydrogen peroxide (hydrogen peroxide).Described organic oxidizing agent can be selected from least one in benzoyl peroxide, tetrafluoro boric acid nitrous.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, according to the difference of conductive high polymer monomer concentration, the electric current of electrochemically oxidative polymerization can be 10mA ~ 100mA, and the time of electrochemically oxidative polymerization can be 5h ~ 20h.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, the ratio of the mole of described oxidant and described monomer can be (1 ~ 5): 1.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described negative active core-shell material can be selected from Si, Sn, SiO x(0<x<2), SnO y(0≤y≤2), Si and at least one are selected from the one in the alloy material of the element in Ti, Fe, Co, Ni and Cu.Alloy material can comprise TiSi 2phase and Si phase.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, the preparation process of cathode pole piece can be: coat on negative current collector by the cathode size containing described conducting polymer and deionized water or 1-METHYLPYRROLIDONE (NMP) and negative active core-shell material, carry out copolymerzation with cross-linking reaction, post-drying, form cathode membrane, anticathode collector carries out roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug together with the cathode membrane on it afterwards, makes cathode pole piece.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, according to the difference of contained crosslinkable groups, described monomer can carry out copolymerzation with cross-linking reaction at different conditions preparing in cathode pole piece process.
When the crosslinkable groups of described monomer is a reactive silicon group, cathode size also can containing the organo-metallic compound as catalyst.Described organo-metallic compound can be selected from least one in dibutyltin diacetate, tetra isopropyl titanium.The weight of described organo-metallic compound can be 0.01% ~ 3% of the weight of conducting polymer.
When the crosslinkable groups of described monomer be alkylene, the ketone containing alkylene, the ether containing alkylene, the ester containing alkylene, the acid amides containing alkylene or containing the aromatic radical of alkylene time, in a kind of mode, cathode size also can contain radical initiator.The optional at least one in organic per-compounds, azo-compound of radical initiator.Described organic per-compounds can be selected from least one in benzoyl hydroperoxide, benzoyl peroxide, peroxide cyclohexanone.Azo-compound can comprise 2,2 '-azodiisobutyronitrile, 2, at least one in 2 '-azo two (2-methyl propanamide) dihydrate.The weight of described radical initiator can be 0.1% ~ 5% of the weight of conducting polymer.
When the crosslinkable groups of described monomer be alkylene, the ketone containing alkylene, the ether containing alkylene, the ester containing alkylene, the acid amides containing alkylene or containing the aromatic radical of alkylene time, in a further mode of operation, cathode size also can contain light trigger, and copolymerzation with cross-linking reaction is undertaken by Ultraviolet radiation.Light trigger can be selected from least one in 2,2-diethoxy acetophenone, dimethoxybenzoin, benzophenone.The weight of described light trigger can be 0.1% ~ 5% of the weight of conducting polymer.
When the crosslinkable groups of described monomer is halogen, cathode size also can contain crosslinking agent.Crosslinking agent can be selected from least one in polyamines class, polythiol class, thiourea.Polyamine compounds can be selected from least one in trien, dimethylaminopropylamine.Polythiol compounds can be selected from least one in 1,10-mercaptan in the last of the ten Heavenly stems two, 2,3-disulfide group pyrazines.The weight of described crosslinking agent can be 0.1% ~ 10% of the weight of conducting polymer.
When the crosslinkable groups of described monomer is hydroxyl, cathode size also can contain crosslinking agent and catalyst.Crosslinking agent can be selected from least one in multi-carboxylic acid, polyisocyanates compounds.Catalyst can be organotin catalysts.Multi-carboxylic acid's compound can be selected from least one in 1,6-adipic acid, 1, 4-succinic acid.Polyisocyanates compounds is optional from 1, at least one in hexamethylene-diisocyanate, Isosorbide-5-Nitrae-Ding two cyanate ester.Organotin catalysts can be selected from least one in dibutyl tin laurate, stannous octoate.The weight of described crosslinking agent can be 0.1% ~ 15% of the weight of conducting polymer.The weight of described catalyst can be 0.1% ~ 10% of the weight of conducting polymer.
In the cathode pole piece of lithium rechargeable battery according to a first aspect of the present invention, described cathode membrane also can comprise inorganic conductive agent.Described inorganic conductive agent can be selected from least one in graphite, carbon black, conductive fiber and metal dust.Graphite can be selected from least one in native graphite, Delanium.Carbon black can be selected from least one in acetylene black, Ketjen black.Conductive fiber can be selected from least one in carbon fiber, metallic fiber.Metal dust can be selected from least one in copper powder, nickel powder.The consumption of inorganic conductive agent is not particularly limited, and be preferably: be 100 parts by weight with negative active core-shell material, inorganic conductive agent can be 0.1 weight portion ~ 10 weight portion.
Secondly lithium rechargeable battery is according to a second aspect of the present invention described.
Lithium rechargeable battery according to a second aspect of the present invention, comprising: anode pole piece, comprises plus plate current-collecting body, is arranged on plus plate current-collecting body and comprises the positive pole diaphragm of positive electrode active materials; Cathode pole piece; Barrier film, is interval between anode pole piece and cathode pole piece; And electrolyte, comprise lithium salts and non-aqueous organic solvent.Described cathode pole piece is the cathode pole piece of the lithium rechargeable battery described in first aspect present invention.
In lithium rechargeable battery according to a second aspect of the present invention, described positive electrode active materials can be selected from the one in layered lithium metal oxides, spinel structure lithium metal oxide, lithium metal pentafluoride sulfate, lithium metal vanadate, lithium metal silicate and lithium metal phosphates.Layered lithium metal oxides can be selected from least one in cobalt acid lithium (LCO), nickel-cobalt-manganese ternary material (NMC).Spinel structure lithium metal oxide can be LiMn2O4 (LiMn 2o 4).Lithium metal phosphates can be LiFePO4 (LFP).Lithium metal pentafluoride sulfate can be fluoridizes cobaltous sulfate lithium (LiCoFSO 4).Lithium metal vanadate can be vanadic acid nickel lithium (LiNiVO 4).Lithium metal silicate can be ferric metasilicate lithium (Li 2feSiO 4).
In lithium rechargeable battery according to a second aspect of the present invention, described plus plate current-collecting body can be selected from aluminium foil or be coated with the aluminium foil of conductive carbon.
In lithium rechargeable battery according to a second aspect of the present invention, described non-aqueous organic solvent can be selected from one or more in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
In lithium rechargeable battery according to a second aspect of the present invention, described lithium salts can be selected from LiPF 6, LiBF 4, LiCl, LiAlCl 4, LiSbF 6, LiSCN, LiCl, LiCF 3sO 3, LiCF 3cO 2, LiN (CF 3sO 2), LiAsF 6and LiBC 4o 8in one or more.
Following explanation is according to lithium rechargeable battery of the present invention and electrolyte thereof and embodiment, comparative example, and wherein the structure of M1 ~ M21 is as shown in table 1.
Embodiment 1
(1) conducting polymer is prepared
By internal volume be 0.5L three mouthfuls of glass flask in air nitrogen replacement, add ferric trichloride (24g) and chloroform (1L).By monomer M 2(weight average molecular weight 400,30g), monomer M 3(weight average molecular weight 550,10g) and monomer M 1(15g) be dissolved in chloroform (300mL) and be added drop-wise in three mouthfuls of glass flask under constantly stirring.After this mixture at room temperature stirring reaction 20h, be added dropwise in methyl alcohol, isolate conducting polymer by decantation afterwards.By conducting polymer vacuumize 24h at normal temperatures, and then at 100 DEG C vacuumize 10h, obtain 36g conducting polymer P1, weight average molecular weight is 150000.
(2) cathode pole piece is prepared
Be dissolved in NMP by gained conducting polymer, add the Si powder being coated with carbon as negative active core-shell material, the acetylene black as conductive agent and be used as 2 of initator, 2 '-azodiisobutyronitrile, fully mixes and makes slurry.Wherein the amount of conducting polymer is every 100 weight portion Si powder is 3 weight portions, and the amount of acetylene black is every 100 weight portion Si powder is 5 weight portions, 2, and the consumption of 2 '-azodiisobutyronitrile is every 100 weight portion conducting polymer 2 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, cross-linking reaction 10h is carried out at 60 DEG C, forced air drying 20h at 85 DEG C again, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared: by positive electrode active materials cobalt acid lithium (LiCoO 2), 90:5:5 and solvent N-methyl pyrilidone fully mix and make slurry in mass ratio for binding agent Kynoar (PVDF), conductive agent conductive black, then slurry is uniformly coated on aluminium foil both sides, forced air drying 20h at 85 DEG C again, form positive pole diaphragm, carry out roll-in, trimming, cut-parts, itemize, vacuum drying, welding positive pole ear afterwards, make anode pole piece.
(4) lithium rechargeable battery is assembled
The cathode pole piece of above-mentioned preparation, anode pole piece, thickness is used to be PE individual layer barrier film, the LiPF of 8 μm 6lithium rechargeable battery A is assembled into using the solution that the weight ratio of 8:92 is formulated as electrolyte with non-aqueous organic solvent (ethylene carbonate: diethyl carbonate: methyl ethyl carbonate: ethenylidene carbonic ester=8:85:5:2).
Embodiment 2
(1) conducting polymer is prepared
By internal volume be 0.5L three mouthfuls of glass flask in air nitrogen replacement, add ferric trichloride (27g)) and chloroform (1L).By monomer M 20(weight average molecular weight 400,30g), monomer M 5(weight average molecular weight 400,8g) and monomer M 4(30g) be dissolved in chloroform (300mL) and be added drop-wise in three mouthfuls of glass flask under constantly stirring.After this mixture at room temperature stirring reaction 16h, be added dropwise in methyl alcohol, isolate conducting polymer by decantation afterwards.By conducting polymer vacuumize 24h at normal temperatures, then vacuumize 10h at 100 DEG C, obtain 50g conducting polymer P2, weight average molecular weight is 500000.
(2) cathode pole piece is prepared
Gained conducting polymer is dissolved in NMP, adds the Si powder being coated with carbon as negative active core-shell material, the acetylene black as conductive agent and be used as the trien of crosslinking agent, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion Si powder is 2 weight portions, and the amount of acetylene black is every 100 weight portion Si powder is 5 weight portions, and the consumption of trien is every 100 weight portion conducting polymer 1 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, cross-linking reaction 10h is carried out at 60 DEG C, forced air drying 20h at 85 DEG C again, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery D of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 2.
Embodiment 3
(1) conducting polymer is prepared
By internal volume be 0.5L three mouthfuls of glass flask in air nitrogen replacement, add ferric trichloride (27g) and chloroform (1L).By monomer M 8(weight average molecular weight 750,30g), monomer M 7(weight average molecular weight 600,12g) and monomer M 6(25g) be dissolved in chloroform (300mL) and be added drop-wise in three mouthfuls of glass flask under constantly stirring.After this mixture at room temperature stirring reaction 40h, be added dropwise in methyl alcohol, isolate conducting polymer by decantation afterwards.By conducting polymer vacuumize 24h at normal temperatures, then vacuumize 10h at 100 DEG C, obtain 48g conducting polymer P3, weight average molecular weight is 70000.
(2) cathode pole piece is prepared
Gained conducting polymer is dissolved in NMP, adds the Si powder being coated with carbon as negative active core-shell material, the acetylene black as conductive agent and be used as the dibutyltin diacetate of catalyst, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion Si powder is 5 weight portions, and the amount of acetylene black is every 100 weight portion Si powder is 5 weight portions, and the consumption of dibutyltin diacetate is every 100 weight portion conducting polymer 3 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, cross-linking reaction 10h at 60 DEG C, then forced air drying 20h at 85 DEG C, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery F of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 3.
Embodiment 4
(1) conducting polymer is prepared
By internal volume be 0.5L three mouthfuls of glass flask in air nitrogen replacement, add ferric trichloride (27g) and chloroform (1L).By monomer M 8(weight average molecular weight 750,30g) and monomer M 7(weight average molecular weight 600,8g) be dissolved in chloroform (300mL) and be added drop-wise in three mouthfuls of glass flask under constantly stirring.After this mixture at room temperature stirring reaction 40h, be added dropwise in methyl alcohol, isolate conducting polymer by decantation afterwards.By conducting polymer vacuumize 24h at normal temperatures, then vacuumize 10h at 100 DEG C, obtain 29g conducting polymer P4, weight average molecular weight is 10000.
(2) cathode pole piece is prepared
Gained conducting polymer is dissolved in NMP, adds the Si powder being coated with carbon as negative active core-shell material, the acetylene black as conductive agent and be used as the dibutyltin diacetate of catalyst, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion Si powder is 5 weight portions, and the amount of acetylene black is every 100 weight portion Si powder is 5 weight portions, and the consumption of dibutyltin diacetate is every 100 weight portion conducting polymer 3 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, cross-linking reaction 10h at 60 DEG C, then forced air drying 20h at 85 DEG C, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery H of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 4.
Embodiment 5
(1) conducting polymer is prepared
By internal volume be 0.5L three mouthfuls of glass flask in air nitrogen replacement, add ferric trichloride (27g) and chloroform (1L).By monomer M 8(weight average molecular weight 750,37.5g), monomer M 3(weight average molecular weight 600,11g) and monomer M 4(5.4g) be dissolved in chloroform (300mL) and be added drop-wise in three mouthfuls of glass flask under constantly stirring.After this mixture at room temperature stirring reaction 40h, be added dropwise in methyl alcohol, isolate conducting polymer by decantation afterwards.By conducting polymer vacuumize 24h at normal temperatures, then vacuumize 10h at 100 DEG C, obtain 29g conducting polymer P5, weight average molecular weight is 2000000.
(2) cathode pole piece is prepared
Be dissolved in NMP by gained conducting polymer, add the Si powder being coated with carbon as negative active core-shell material, the acetylene black as conductive agent and be used as 2 of initator, 2 '-azo two (2-methyl propanamide), fully mixes and makes slurry.Wherein the amount of conducting polymer is every 100 weight portion Si powder is 5 weight portions, and the amount of acetylene black is every 100 weight portion Si powder is 5 weight portions, 2, and the consumption of 2 '-azo two (2-methyl propanamide) is every 100 weight portion conducting polymer 3 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, cross-linking reaction 10h is carried out at 60 DEG C, then forced air drying 20h at 85 DEG C, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery I of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 5.
Embodiment 6
(1) conducting polymer is prepared
By internal volume be 0.5L three mouthfuls of glass flask in air nitrogen replacement, add monomer M 10(weight average molecular weight 750,45g), monomer M 11(weight average molecular weight 700,1.4g), monomer M 9(36g), hydrogen peroxide (9.81g) and acetonitrile (300mL).After this mixture at room temperature stirring reaction 40h, be added dropwise in methyl alcohol, isolate conducting polymer by decantation afterwards.By conducting polymer vacuumize 24h at normal temperatures, then vacuumize 10h at 100 DEG C, obtain 45g conducting polymer P6, weight average molecular weight is 350000.
(2) cathode pole piece is prepared
Above-mentioned obtained conducting polymer is dissolved in deionized water, adds the SiO as negative active core-shell material x(0<x<2) Ketjen black, as conductive agent, as crosslinking agent 1, hexamethylene-diisocyanate and the dibutyl tin laurate as catalyst, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion SiO xpowder is 1 weight portion, and the amount of Ketjen black is every 100 weight portion SiO xpowder 3 weight portion, 1, the consumption of hexamethylene-diisocyanate is every 100 weight portion conducting polymer 1 weight portions, and the consumption of dibutyl tin laurate is every 100 weight portion conducting polymer 0.1 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, at 50 DEG C, manage 0.5h carry out cross-linking reaction, forced air drying 20h at 75 DEG C, vacuumize 24h at 75 DEG C again, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery J of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 6.
Embodiment 7
(1) conducting polymer is prepared
By internal volume be 1L electrolysis tank in air nitrogen replacement, add monomer M 12(weight average molecular weight 800,4g), monomer M 13(weight average molecular weight 750,0.75g), monomer M 9(1g), TBuA hexafluorophosphate (9.81g) and acetonitrile (300mL).Take surface area as 100cm 2two pieces of glassy carbon electrodes be work electrode and to electrode, take saturated calomel electrode as reference electrode, by this mixture with the electric current Constant Electric Current of 100mA polymerization 5h.Be separated from work electrode by conducting polymer, vacuumize 24h, then vacuumize 10h at 100 DEG C at normal temperatures after acetonitrile cleaning, obtain 3.8g conducting polymer P7, weight average molecular weight is 120000.
(2) cathode pole piece is prepared
Above-mentioned obtained conducting polymer is dissolved in deionized water, adds the SiO as negative active core-shell material x(0<x<2), as conductive agent Ketjen black and be used as 2,2-diethoxy acetophenones of light trigger, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion SiO xpowder 3 weight portion, the amount of Ketjen black is every 100 weight portion SiO xpowder 5 weight portion, the consumption of 2,2-diethoxy acetophenone is every 100 weight portion conducting polymer 1 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, (light intensity 300mW/cm under ultraviolet light 2, wavelength 365nm) and carry out cross-linking reaction 0.5h, forced air drying 20h at 75 DEG C, vacuumize 24h at 75 DEG C again, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery M of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 7.
Embodiment 8
(1) conducting polymer is prepared
By internal volume be 1L electrolysis tank in air nitrogen replacement, add monomer M 21(weight average molecular weight 400,3.2g), monomer M 3(weight average molecular weight 550,0.8g), monomer M 14(0.09g), TBuA hexafluorophosphate (9.81g) and acetonitrile (300mL).Take surface area as 100cm 2two pieces of glassy carbon electrodes be work electrode and to electrode, take saturated calomel electrode as reference electrode, by this mixture with the electric current Constant Electric Current of 100mA polymerization 5h.Be separated from work electrode by conducting polymer, vacuumize 24h, then vacuumize 10h at 100 DEG C at normal temperatures after acetonitrile cleaning, obtain 3.2g conducting polymer P8, weight average molecular weight is 100000.
(2) cathode pole piece is prepared
Above-mentioned obtained conducting polymer is dissolved in NMP, adds the SiO as negative active core-shell material x(0<x<2), as conductive agent Ketjen black and be used as the benzoyl peroxide of initator, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion SiO xpowder is 3 weight portions, and the amount of Ketjen black is every 100 weight portion SiO xpowder 5 weight portion, the consumption of benzoyl peroxide is every 100 weight portion conducting polymer 0.1 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, cross-linking reaction 3h is carried out at 70 DEG C, at 85 DEG C after forced air drying 20h, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery N of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 8.
Embodiment 9
(1) conducting polymer is prepared
By internal volume be 1L electrolysis tank in air nitrogen replacement, add M16(weight average molecular weight 500,1g), M17(weight average molecular weight 600,3.6g), monomer M 15(1.2g), TBuA tetrafluoroborate (5.1g) and oxolane (200mL).Take surface area as 100cm 2two pieces of glassy carbon electrodes be work electrode and to electrode, take saturated calomel electrode as reference electrode, by this mixture with the electric current Constant Electric Current of 10mA polymerization 20h.Be separated from work electrode by conducting polymer, vacuumize 24h, then vacuumize 10h at 60 DEG C at normal temperatures after oxolane cleaning, obtain 4.8g conducting polymer P9, weight average molecular weight is 80000.
(2) cathode pole piece is prepared
Above-mentioned gained conducting polymer is dissolved in NMP, adds the SnO as negative active core-shell material y(0≤y≤2) and the dimethoxybenzoin as light trigger, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion SnO ypowder 5 weight portion, dimethoxybenzoin is every 100 weight portion conducting polymer 1 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, (light intensity 150mW/cm under ultraviolet light 2, wavelength 365nm) and carry out cross-linking reaction 1h, forced air drying 20h at 85 DEG C, vacuumize 24h at 75 DEG C afterwards, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery O of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 9.
Embodiment 10
(1) conducting polymer is prepared
By internal volume be 1L electrolysis tank in air nitrogen replacement, add M18(weight average molecular weight 500,3.2g), M19(weight average molecular weight 600,0.9g), monomer M 1(0.2g), TBuA tetrafluoroborate (5.1g) and carrene (200mL).Take surface area as 100cm 2two pieces of glassy carbon electrodes be work electrode and to electrode, take saturated calomel electrode as reference electrode, by this mixture with the electric current Constant Electric Current of 10mA polymerization 18h.Be separated from work electrode by gained conducting polymer, vacuumize 24h, then vacuumize 10h at 60 DEG C at normal temperatures after oxolane cleaning, obtain 2.8g conducting polymer P10, weight average molecular weight is 150000.
(2) cathode pole piece is prepared
Above-mentioned gained conducting polymer is dissolved in NMP, adds the SnO as negative active core-shell material y(0≤y≤2) and the tetra isopropyl titanium as catalyst, fully mix and make slurry.Wherein the amount of conducting polymer is every 100 weight portion SnO ypowder is 5 weight portions, and tetra isopropyl titanium is every 100 weight portion conducting polymer 1 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, cross-linking reaction 1h is carried out at 50 DEG C, at 85 DEG C after forced air drying 20h, vacuumize 24h at 75 DEG C again, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery R of embodiment 1, unlike the use of cathode pole piece obtained in embodiment 10.
Comparative example 1
(1) conducting polymer is prepared
Method according to embodiment 1 prepares conducting polymer.
(2) cathode pole piece is prepared
Method according to embodiment 1 prepares cathode pole piece, unlike preparing in cathode pole piece process do not add as cross-linked evocating agent 2,2 '-azodiisobutyronitrile.
(3) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery B of embodiment 1, unlike the use of cathode pole piece obtained in comparative example 1.
Comparative example 2
(1) cathode pole piece is prepared
Non-conductive polymer PVDF is dissolved in NMP, adds the Si powder being coated with carbon as negative active core-shell material and the acetylene black as conductive agent, fully mix and make slurry.Wherein the amount of PVDF is every 100 weight portion Si powder is 1 weight portion, and the amount of acetylene black is every 100 weight portion Si powder is 5 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, forced air drying 20h at 85 DEG C, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(2) anode pole piece is prepared
Method according to embodiment 1 prepares anode pole piece.
(3) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery C of embodiment 1, unlike the use of the cathode pole piece that comparative example 2 is obtained.
Comparative example 3
(1) conducting polymer is prepared
Method according to embodiment 2 prepares conducting polymer.
(2) cathode pole piece is prepared
Method according to embodiment 2 prepares cathode pole piece, unlike preparing in cathode pole piece process the trien do not added as crosslinking agent.
(3) anode pole piece is prepared
Method according to embodiment 2 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery E of embodiment 2, unlike the use of the cathode pole piece that comparative example 3 is obtained.
Comparative example 4
(1) conducting polymer is prepared
Method according to embodiment 3 prepares conducting polymer.
(2) cathode pole piece is prepared
Method according to embodiment 3 prepares cathode pole piece, unlike preparing in cathode pole piece process the dibutyltin diacetate do not added as crosslinking catalyst.
(3) anode pole piece is prepared
Method according to embodiment 3 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery G of embodiment 3, unlike the use of the cathode pole piece that comparative example 4 is obtained.
Comparative example 5
(1) conducting polymer is prepared
Method according to embodiment 6 prepares conducting polymer.
(2) cathode pole piece is prepared
Method according to embodiment 6 prepares cathode pole piece, unlike preparing in cathode pole piece process do not add as crosslinking agent 1, and hexamethylene-diisocyanate and the dibutyl tin laurate as catalyst.
(3) anode pole piece is prepared
Method according to embodiment 6 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery K of embodiment 6, unlike the use of cathode pole piece obtained in comparative example 5.
Comparative example 6
(1) cathode pole piece is prepared
Non-conductive polymer SBR and CMC is dissolved in deionized water, adds the SiO being coated with carbon as negative active core-shell material x(0<x<2) powder and the Ketjen black as conductive agent, fully mix and make slurry.Wherein the amount of SBR is every 100 weight portion SiO xpowder is 2 weight portions, and the amount of CMC is every 100 weight portion SiO xpowder is 3 weight portions, and the amount of Ketjen black is every 100 weight portion SiO xpowder is 3 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, at 75 DEG C after forced air drying 20h, vacuumize 24h at 75 DEG C again, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(2) anode pole piece is prepared
Method according to embodiment 6 prepares anode pole piece.
(3) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery L of embodiment 6, unlike the use of cathode pole piece obtained in comparative example 6.
Comparative example 7
(1) conducting polymer is prepared
Method according to embodiment 9 prepares conducting polymer.
(2) cathode pole piece is prepared
Method according to embodiment 9 prepares cathode pole piece, unlike preparing in cathode pole piece process the dimethoxybenzoin do not added as light trigger.
(3) anode pole piece is prepared
Method according to embodiment 9 prepares anode pole piece.
(4) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery P of embodiment 9, unlike the use of cathode pole piece obtained in comparative example 7.
Comparative example 8
(1) cathode pole piece is prepared
Non-conductive polymer PVDF is dissolved in NMP, adds the SnO being coated with carbon as negative active core-shell material y(0≤y≤2) powder, fully mixes and makes slurry.Wherein the amount of PVDF is every 100 weight portion SnO ypowder is 5 weight portions.Described slurry is coated in 12 μm of thick Copper Foil both sides, forced air drying 20h at 85 DEG C, form cathode membrane, afterwards together with the cathode membrane on it, roll-in, trimming, cut-parts, itemize, vacuum drying, welding negative lug are carried out to Copper Foil, make cathode pole piece.
(2) anode pole piece is prepared
Method according to embodiment 9 prepares anode pole piece.
(3) lithium rechargeable battery is assembled
According to the method assembling lithium rechargeable battery Q of embodiment 9, unlike the use of cathode pole piece obtained in comparative example 8.
Test process and the test result of lithium rechargeable battery of the present invention are finally described.
(1) cycle performance test
Often group gets 4 lithium rechargeable batteries, at normal temperatures with 1C constant current charge to 4.3V, then constant voltage charge is to 0.05C, to leave standstill after 0.5h with 1C constant-current discharge to 3.0V, then leaves standstill 0.5h, complete a charge and discharge cycles process, record primary discharge capacity.Circulate 500 times with this.
The capability retention that lithium rechargeable battery is the N time=(discharge capacity/primary discharge capacity of the N time) × 100%.
(2) high-rate charge-discharge capability test
Often group gets 4 lithium rechargeable batteries, at normal temperatures with 3C constant current charge to 4.3V, then after constant voltage charge to 0.05C, to leave standstill after 0.5h with 3C constant-current discharge to 3.0V, obtain discharge capacity during lithium rechargeable battery 3C discharge and recharge.
Often group gets 4 lithium rechargeable batteries, at normal temperatures with 1C constant current charge to 4.3V, then after constant voltage charge to 0.05C, to leave standstill after 0.5h with 1C constant-current discharge to 3.0V, obtain discharge capacity during lithium rechargeable battery 1C discharge and recharge.
High-multiplying power discharge Capacity Ratio=(discharge capacity during discharge capacity during 3C discharge and recharge/1C discharge and recharge) × 100% of lithium rechargeable battery.
Table 1 provides the molecular structure of monomer M 1-M21.
Table 2 provides parameter and the performance test results of embodiment 1-10 and comparative example 1-8.
(1) cycle performance test result analysis
As can be seen from Table 2, lithium rechargeable battery C, L and Q(comparative example 2, comparative example 6, comparative example 8 relative to using non-conductive polymer as binding agent), the cycle performance of the lithium rechargeable battery using conducting polymer of the present invention to assemble as binding agent is better, especially can also keep higher capability retention after 500 circulations, there is obviously advantage.This is because conducting polymer greatly can improve electrical contact in cyclic process between negative active core-shell material and negative current collector, thus reduces the capacity attenuation of lithium rechargeable battery and improve its cycle performance.
Relative to the conducting polymer used without crosslinking Treatment as lithium rechargeable battery B, E, G, K and P(comparative example 1, comparative example 3-5, the comparative example 7 of binding agent), use lithium rechargeable battery A, D, F, J and O(embodiment 1-3, embodiment 6, the embodiment 9 of the conducting polymer through crosslinking Treatment) higher at the capability retention after 500 circulations.This be due to crosslinking Treatment after conducting polymer can form conductive polymer network, greatly improve long-range conductive capability and the adhesion strength of conducting polymer, thus suppress the volumetric expansion of negative active core-shell material, improve the cycle performance of lithium rechargeable battery.
When not adding inorganic conductive agent in cathode pole piece, use non-conductive polymer PVDF as the lithium rechargeable battery Q(comparative example 8 of binding agent) cannot charge and discharge cycles be carried out completely.Even do not contain any inorganic conductive agent in cathode pole piece but the lithium rechargeable battery P(comparative example 7 of employing P9), also still can carry out charge and discharge cycles.But use the conducting polymer through crosslinking Treatment as the lithium rechargeable battery O of binding agent and R(embodiment 9 and embodiment 10) cycle performance better.Even if this is owing to not adding inorganic conductive agent, the use of conducting polymer still can ensure that the cathode pole piece containing negative active core-shell material has enough conductive capabilities, therefore conducting polymer of the present invention is after crosslinking Treatment, partly can substitute the inorganic conductive agent in the cathode pole piece of lithium rechargeable battery even completely, thus greatly improve the energy density of lithium rechargeable battery, and then improve the cycle performance of lithium rechargeable battery.In addition, because the P10 in embodiment 10 is the conducting polymer containing polyamine side chain, its structure is stable not, and therefore the cycle performance of lithium rechargeable battery is slightly poorer than using the embodiment 9 of P9.
As can be seen from the contrast of embodiment 1-5, the conducting polymer of same kind under the same polymerization conditions, monomer suitably adds the getable higher molecular weight of substituting group.The molecular weight of conducting polymer is larger, and its cementitiousness is stronger, and long distance conductive capability is stronger, and the cycle performance of lithium rechargeable battery is better.But when the molecular weight of conducting polymer is too low (embodiment 4), even if the conducting polymer after crosslinked can not play enough conductive capabilities and cementitiousness in lithium rechargeable battery, thus effectively can not improve the cycle performance of lithium rechargeable battery; When conductive polymer molecules amount is too high (embodiment 5), solubility is less in a solvent for it, thus cause it can not well be disperseed in cathode pole piece manufacturing process, enough conductive capabilities and cementitiousness can not be played in lithium rechargeable battery, thus the cycle performance of lithium rechargeable battery is deteriorated on the contrary.
As can be seen from the contrast of embodiment 6 and embodiment 7, use the monomer of same kind, chemical oxidising polymerisation is higher relative to the molecular weight of the conducting polymer that electrochemically oxidative polymerization obtains, and the cycle performance of lithium rechargeable battery is better.Meanwhile, because P7 in embodiment 7 is pyroles conducting polymer, itself structure is stable not, and the cycle performance therefore in lithium rechargeable battery is slightly poor.
In embodiment 8, because P8 has the highest conductivity, even if its molecular weight is not high, the cycle performance of lithium rechargeable battery also greatly can be improved.
(2) high-rate charge-discharge capability test result analysis
As can be seen from Table 2, lithium rechargeable battery C, L and Q(comparative example 2, comparative example 6, comparative example 8 relative to using non-conductive polymer as binding agent), use conducting polymer obviously to improve as the high rate performance of the lithium rechargeable battery of binding agent.This is because conducting polymer greatly can improve electronics and ionic conduction in cathode pole piece, thus improves the high rate performance of lithium rechargeable battery.
Relative to the conducting polymer used without crosslinking Treatment as lithium rechargeable battery B, E, G, K and P(comparative example 1, comparative example 3-5, the comparative example 7 of binding agent), use lithium rechargeable battery A, D, F, J and O(embodiment 1-3, embodiment 6, the embodiment 9 of the conducting polymer through crosslinking Treatment) there is more excellent high rate performance.This is because the conducting polymer through crosslinking Treatment can form conductive polymer network, greatly improves the long-range conductive capability of conducting polymer, thus improves the electrical contact between negative active core-shell material, and then improves the high rate performance of lithium rechargeable battery.
When not adding any inorganic conductive agent in cathode pole piece, use non-conductive polymer PVDF as the lithium rechargeable battery Q(comparative example 8 of binding agent) cannot charge and discharge cycles be carried out completely.Even if do not contain any inorganic conductive agent in cathode pole piece but the lithium rechargeable battery P(comparative example 7 of employing P9), still can normally use.But use the conducting polymer through crosslinking Treatment as the lithium rechargeable battery O of binding agent and R(embodiment 9 and embodiment 10) high rate performance better.This is because conducting polymer of the present invention is after crosslinking Treatment, there is good short distance and long-range conductive capability, partly can substitute the inorganic conductive agent in the cathode pole piece of lithium rechargeable battery even completely, improve the energy density of lithium rechargeable battery, and then improve the high rate performance of lithium rechargeable battery.In addition, because the P10 in embodiment 10 is the conducting polymer containing polyamine side chain, its structure is stable not, and therefore the high rate performance of lithium rechargeable battery is slightly poorer than using the embodiment 9 of P9.
As can be seen from the contrast of embodiment 1-5, the conducting polymer of same kind under the same polymerization conditions, monomer suitably adds the getable higher molecular weight of substituting group.The molecular weight of conducting polymer is larger, and its cementitiousness is stronger, and long-range conductive capability is stronger, and the high rate performance of lithium rechargeable battery is better.But when the molecular weight of conducting polymer is too low (embodiment 4), even if the conducting polymer after crosslinked can not play enough conductive capabilities and cementitiousness in lithium rechargeable battery, thus effectively can not improve the high rate performance of lithium rechargeable battery; When conductive polymer molecules amount is too high (embodiment 5), solubility is less in a solvent for it, thus cause it can not well be disperseed in cathode pole piece manufacturing process, enough conductive capabilities and cementitiousness can not be played in lithium rechargeable battery, thus make the high rate performance of lithium rechargeable battery start on the contrary to be deteriorated.
As can be seen from the contrast of embodiment 6 and embodiment 7, use the monomer of same kind, chemical oxidising polymerisation is higher compared to the molecular weight of the conducting polymer that electrochemically oxidative polymerization obtains, and therefore the high rate performance of lithium rechargeable battery is better.Meanwhile, because P7 in embodiment 7 is pyroles conducting polymer, itself structure is stable not, and therefore the high rate performance of lithium rechargeable battery is slightly poor.
In embodiment 8, because P8 has the highest conductivity, even if its molecular weight is not high, the high rate performance of lithium rechargeable battery also greatly can be improved.
The molecular structure of table 1 monomer M 1-M21

Claims (12)

1. a cathode pole piece for lithium rechargeable battery, comprising:
Negative current collector; And
Cathode membrane, to be arranged on negative current collector and to comprise negative active core-shell material, binding agent;
It is characterized in that, described binding agent comprises the conducting polymer by the monomer crosslinked copolymerization with crosslinkable groups, and described monomer comprises the monomer with molecular formula 1 and molecular formula 2 structure;
In molecular formula 1 and molecular formula 2:
The one that P is selected from hydrogen atom, has the alkyl of 1 ~ 12 carbon atom, has the alkoxyl of 1 ~ 12 carbon atom, has the cycloalkyloxy of 1 ~ 12 carbon atom, has the itrile group of 1 ~ 12 carbon atom, has the sulfonate group of 1 ~ 12 carbon atom and have in the carboxylic acid ester groups of 1 ~ 12 carbon atom;
X is selected from S, NR 1, R 1the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom, there is the carboxylic acid ester groups of 1 ~ 12 carbon atom and have in the sulfonate group of 1 ~ 12 carbon atom;
Y is selected from the one in-O-,-C (=O) O-,-C (=O) NH-,-NH-;
Z is selected from O, NR 2, R 2the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom and have in the aromatic radical of 6 ~ 14 carbon atoms;
B is selected from hydrogen atom, the one had in the alkyl of 1 ~ 12 carbon atom;
G is selected from hydrogen atom, reactive silicon group, alkylene, the ketone containing alkylene, the ether containing alkylene, the ester containing alkylene, the acid amides containing alkylene, alkyl containing halogen, hydroxyl or reactive silicon group and containing the one in the aromatic radical of halogen, alkylene, hydroxyl or reactive silicon group;
It is hydrogen atom when B and G is different;
N is the integer between 1 ~ 20.
2. the cathode pole piece of lithium rechargeable battery according to claim 1, is characterized in that, in described conducting polymer:
It is 10% ~ 99.9% that the monomer with molecular formula 1 structure accounts for the overall mole percent of monomer;
It is 0.1% ~ 90% that the monomer with molecular formula 2 structure accounts for the overall mole percent of monomer.
3. the cathode pole piece of lithium rechargeable battery according to claim 1, is characterized in that, described monomer also comprises the monomer with molecular formula 3 structure,
In molecular formula 3:
The one that P is selected from hydrogen atom, has the alkyl of 1 ~ 12 carbon atom, has the alkoxyl of 1 ~ 12 carbon atom, has the cycloalkyloxy of 1 ~ 12 carbon atom, has the itrile group of 1 ~ 12 carbon atom, has the sulfonate group of 1 ~ 12 carbon atom and have in the carboxylic acid ester groups of 1 ~ 12 carbon atom;
X is selected from S, NR 1, R 1the one being selected from hydrogen atom, there is the alkyl of 1 ~ 12 carbon atom, there is the carboxylic acid ester groups of 1 ~ 12 carbon atom and have in the sulfonate group of 1 ~ 12 carbon atom.
4. the cathode pole piece of lithium rechargeable battery according to claim 3, is characterized in that, in described conducting polymer:
It is 10% ~ 99.9% that the monomer with molecular formula 1 structure accounts for the overall mole percent of monomer;
It is 0.1% ~ 90% that the monomer with molecular formula 2 structure accounts for the overall mole percent of monomer;
It is 0% ~ 70% that the monomer with molecular formula 3 structure accounts for the overall mole percent of monomer.
5. the cathode pole piece of the lithium rechargeable battery according to claim 1 or 3, is characterized in that, described conducting polymer accounts for 0.1% ~ 10% of described negative active core-shell material total weight.
6. the cathode pole piece of lithium rechargeable battery according to claim 5, is characterized in that, described conducting polymer accounts for 1% ~ 5% of described negative active core-shell material total weight.
7. the cathode pole piece of the lithium rechargeable battery according to claim 1 or 3, it is characterized in that, described conducting polymer is prepared from through electrochemically oxidative polymerization or chemical oxidising polymerisation by described monomer, and the weight average molecular weight of described conducting polymer is 10000 ~ 2000000.
8. the cathode pole piece of lithium rechargeable battery according to claim 7, is characterized in that, the weight average molecular weight of described conducting polymer is 50000 ~ 500000.
9. the cathode pole piece of lithium rechargeable battery according to claim 1, is characterized in that, described negative active core-shell material is selected from Si, Sn, SiO x, SnO y, Si and at least one be selected from one in the alloy material of the element in Ti, Fe, Co, Ni and Cu, wherein, 0<x<2,0<y≤2.
10. the cathode pole piece of the lithium rechargeable battery according to claim 1 or 3, it is characterized in that, the preparation process of cathode pole piece is, cathode size containing described conducting polymer and deionized water or 1-METHYLPYRROLIDONE (NMP) and negative active core-shell material is coated on negative current collector, carries out copolymerzation with cross-linking reaction.
The cathode pole piece of 11. lithium rechargeable batteries according to claim 10, is characterized in that,
When the crosslinkable groups of described monomer is a reactive silicon group, cathode size is also containing the organo-metallic compound as catalyst;
When the crosslinkable groups of described monomer be alkylene, the ketone containing alkylene, the ether containing alkylene, the ester containing alkylene, the acid amides containing alkylene or containing the aromatic radical of alkylene time, cathode size is also containing radical initiator or light trigger;
When the crosslinkable groups of described monomer is halogen, cathode size is also containing crosslinking agent;
When the crosslinkable groups of described monomer is hydroxyl, cathode size is also containing crosslinking agent and catalyst.
12. 1 kinds of lithium rechargeable batteries, comprising:
Anode pole piece, comprises plus plate current-collecting body, is arranged on plus plate current-collecting body and comprises the positive pole diaphragm of positive electrode active materials;
Cathode pole piece;
Barrier film, is interval between anode pole piece and cathode pole piece; And
Electrolyte, comprises lithium salts and non-aqueous organic solvent;
It is characterized in that,
The cathode pole piece of the lithium rechargeable battery of described cathode pole piece according to any one of claim 1-11.
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