CN102487141A - Cathode material of lithium ion battery and battery - Google Patents
Cathode material of lithium ion battery and battery Download PDFInfo
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- CN102487141A CN102487141A CN2010105789152A CN201010578915A CN102487141A CN 102487141 A CN102487141 A CN 102487141A CN 2010105789152 A CN2010105789152 A CN 2010105789152A CN 201010578915 A CN201010578915 A CN 201010578915A CN 102487141 A CN102487141 A CN 102487141A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a cathode material of a lithium ion battery. The cathode material contains active substance and conductive agent, wherein the conductive agent comprises a first conductive agent and a second conductive agent; the first conductive agent is a conductive polymer containing polar groups, and the second conductive agent is one or more selected from carbon black, graphite, carbon fiber, carbon nanotube, nickel carbonyl powder, copper powder, iron powder, zinc powder and aluminium powder. The invention also provides a lithium ion battery. During a slurry preparation process, polar groups facilitate hydrogen bond formation on the second conductive agent and the anode active substance surface and enhance disperse degree of the second conductive agent and the anode active substance in a solvent, so that the slurry is more easily coated, and the coating thickness is uniform; and the prepared polar sheet has good consistency.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and the battery that uses this positive electrode.
Background technology
Lithium ion battery has the discharge voltage height, energy density is high and recycle long characteristics of life-span, therefore in field of portable electronic devices, is used widely, and receives the favor like some high-tech application fields such as military affairs, space flight, electric automobiles simultaneously.
The lithium ion battery main performance index has battery capacity and cycle performance, and the quality of battery performance depends on electrode material.The tradition lithium battery is made up of positive pole, negative pole, barrier film and electrolyte.Anode material for lithium-ion batteries contains positive active material, conductive agent and binding agent.The tradition lithium ion cell electrode prepares and adds conductive agents such as a certain amount of carbon black, graphite in the process, and adds binding agents such as a certain amount of Kynoar, polytetrafluoroethylene.Add the insulating properties binding agent and need more conductive agent power supply tank discharge, and the conductive agent of adding high-specific surface area requires more binding agent to come machine-shaping.Said conductive agent and binding agent do not possess electro-chemical activity; Thereby cause the relative amount of electroactive substance in electrode lower; Influenced the whole actual specific capacity of electrode, and its content and deployment conditions in electrode high power discharge performance that can influence battery.
There are some researches show; Can be behind interpolation chemistry or the electrochemical doping in electrode material by the conducting polymer that contains the pi-electron conjugated structure of insulator to conductor or semiconductor transformation; As contain polypyrrole, polyaniline, polythiophene, gather the isostructural polymer of furans; Can improve the translational speed of electronics and lithium ion in the lithium ion battery, thereby improve the charge/discharge capacity of battery, also can play the effect of binding agent simultaneously.For example; CN101630728A discloses a kind of preparation method of lithium ion secondary battery electrode; Used the conductive agent of conducting polymer as anode, said battery has obtained the specific capacity higher than traditional lithium rechargeable battery, high power discharge ability and longer life-span; CN101651233A discloses a kind of preparation method of lithium rechargeable battery, and cell positive material adds conducting polymer as binding agent, compares traditional lithium rechargeable battery, and said lithium rechargeable battery has higher battery capacity and better cycle ability.
But the compatibility of above-mentioned conducting polymer and binding agent and solvent is not high; The workability of slurry is bad; The pole piece that applies is in uneven thickness; The batch battery consistency that causes preparing is relatively poor, and existing a large amount of electric tools for example electric motor car etc. all adopt a large amount of battery strings parallel connections that electric power is provided, each item performance of battery pack is the algebraic addition of single battery performance anything but.Less difference between battery; Or even nuance; Can cause the difference of the characteristic such as capacity, internal resistance of each battery unit, can make the big person of capacity always be in that little electric current is shallow to fill the shallow state of putting, and the little person of capacity always be in big electric current super-charge super-discharge state; Performance parameter difference is increasing between the two, and low capacity the person lost efficacy in advance; Or make the big series resistance that becomes power consumption of internal resistance, and it is too high to generate heat easily, shortens the life-span.In the use of battery pack, the temperature of each battery unit, voltage, electric current etc. are all different, and after work a period of time, the consistency of battery pack continues to worsen certainly, causes the efficiency of battery to be reduced to the level that can't accept and continue to use rapidly at last.The ultimate aim that improves consistency of battery pack is cost performance, life-span and the fail safe that improves battery pack.
Summary of the invention
In order to improve the consistency of preparation battery pole piece, make battery obtain high power capacity and outstanding cycle performance simultaneously, a kind of anode material for lithium-ion batteries is provided and uses the battery of this positive electrode.
The present invention provides a kind of anode material for lithium-ion batteries; This positive electrode contains positive active material and conductive agent; Wherein, Said conductive agent comprises first conductive agent and second conductive agent, and said first conductive agent is the conducting polymer that contains polar group, and said second conductive agent is one or more in carbon black, graphite, carbon fiber, CNT, carbonyl nickel powder, copper powder, iron powder, zinc powder and the aluminium powder.
The present invention also provides a kind of lithium ion battery; This lithium ion battery comprises battery case, pole piece and electrolyte; Said pole piece and electrolyte are sealed in the battery case; Said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, contained positive electrode is an anode material for lithium-ion batteries provided by the invention in the said positive pole.
Contain the conducting polymer that first conductive agent promptly contains polar group in the positive electrode provided by the invention; In the slurry process for preparation; Polar group helps forming hydrogen bond with second conductive agent and positive active material surface, strengthens their degrees of scatter in solvent, makes slurry more be prone to apply; Coating thickness is even, the pole piece high conformity of preparation.The result is as shown in table 2, and the battery that the conducting polymer of polar functionalities is made is in discharge capacity, and the consistency in voltage and the internal resistance all is superior to not adding conducting polymer and adds the not battery of the conducting polymer making of polar functionalities.
In addition; The conducting polymer of polar functionalities can substitute part binding agent and conductive agent; Reduce electrochemistry inert component in the battery, and the conducting polymer and the positive active material that contain polar group there is stronger physical action, serves as and conduct electricity fulcrum and be connected lead; Second conductive agent serves as conductive node (particularly under the close situation of the particle diameter of the particle diameter of second conductive agent and anodal utmost point active material); In electrode, form effective conductive network, reduced the internal resistance of cell, thereby the battery of preparation has height ratio capacity and excellent cycle performance.Specific capacity like embodiment 4 and Comparative Examples 1,2 obtained lithium ion batteries is respectively 123.0mAh/g, 114.4mAh/g, 118.0mAh/g; The cell voltage discharge platform is respectively 3.39V, 3.15V, 3.26V; Circulating, capability retention is respectively 92.2%, 91.2%, 91.4% after 500 times.The lithium ion battery that contains the conducting polymer of being with polar group, with respect to not containing conducting polymer or contain the lithium ion battery of the conducting polymer of not being with polar group, its battery specific capacity, discharge voltage and repeatedly circulation back capability retention be improved.
Embodiment
Anode material for lithium-ion batteries provided by the invention contains positive active material and conductive agent; Wherein, Said conductive agent comprises first conductive agent and second conductive agent; Said first conductive agent is the conducting polymer that contains polar group, and said second conductive agent is one or more in carbon black, graphite, carbon fiber, CNT, carbonyl nickel powder, copper powder, iron powder, zinc powder and the aluminium powder.
With respect to the positive active material of 100 weight portions, the said content that contains the conducting polymer of polar group can be 0.1～20 weight portion, is preferably 0.5～10 weight portion.
The said conducting polymer that contains polar group can for polyaniline, the polypyrrole that contains polar group, the polythiophene that contains polar group that contain polar group, contain polar group gather furans, contain polar group polyhenylene (gathering) to benzene, contain polar group coalescence benzene, contain polar group the p-phenylene vinylene, contain the polypropylene of polar group and contain one or more of metacetaldehyde of polar group.Said polar group can be arranged in the main chain and/or the side chain of said conducting polymer.Said polar group can for carboxyl (COOH), hydroxyl (OH), halogen (F ,-Cl ,-Br ,-I), nitro (NO
2), amino (NH
2), (O-R, wherein R is preferably C to alkoxyl
2-C
21The straight or branched alkyl), (CO-R, wherein R is preferably C to carbonyl
2-C
21The straight or branched alkyl), ester group (O-CO-R or-CO-O-R, wherein R is preferably C
2-C
21The straight or branched alkyl), amide groups (CO-NH-R or-NH-CO-R, wherein R is preferably C
2-C
21The straight or branched alkyl), in sulfonic group and the organic salt one or more.Said organic salt can be carboxylate, ammonium salt, sulfonate, phosphate etc.The said conducting polymer that contains polar group can be through will containing polar group the monomer polymerization of conducting polymer obtain, the method for polymerization and condition can be identical with the polymerization process of the monomer of the conducting polymer of polar functionalities not.
Among the present invention, said second conductive agent can be in carbon black, graphite, carbon fiber, CNT, carbonyl nickel powder, copper powder, iron powder, zinc powder and the aluminium powder one or more.With respect to the positive active material of 100 weight portions, the content of second conductive agent can be 0.1～20 weight portion, is preferably 0.5～10 weight portion.
Said positive active material can be preferably LiCoO for the conventional various positive active materials that are used for lithium ion battery in this area
2, LiMn
2O
4, LiNiO
2, LiVPO
4, LiCoAlO
2, LiMnCoO
2, LiFe
aM
1-aPO4 (M is Co, Ni, Mn, 0.8≤a≤1), LiCo
xNi
yMn
zO
2In (x+y+z=1,0≤x≤1,0≤y≤1,0≤z≤1) one or more.
Said positive electrode can also contain binding agent; Binding agent can be the various positive binder that are used for lithium ion battery that this area is conventional, is preferably Kynoar, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, butadiene-styrene rubber, gathers methylcellulose, gathers sodium carboxymethylcellulose pyce, in hydroxypropyl methylcellulose and the POLYPROPYLENE GLYCOL one or more.Polyacrylate, polyurethane and epoxy resin can be fluorine-containing.With respect to the positive active material of 100 weight portions, the content of binding agent can be 1～20 weight portion.
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 conventionally known to one of skill in the art, and the viscosity that can be coated with according to the slurry of anodal slurries and the requirement of operability are adjusted.Made then positive electrode slurries slurry is coated in collector (can use any collector body known in the field, for example aluminium foil) and goes up dry compressing tablet, and cut-parts form lithium ion cell positive again.The temperature range of choice of said drying can be 90～150 ℃, can be 10～40min drying time.
Said solvent can be all kinds of solvents known in the field; Be preferably water, N-methyl pyrrolidone (NMP), N; Dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), 1, one or more in 2-propane diols carbonic ester, alcohol, oxolane and the acetone.
Negative pole in the lithium ion battery of the present invention can be various negative poles known in the field.Said negative pole contains the negative material on collector and the coated collector, and said collector can adopt the various collectors that are used for lithium ion battery in the prior art, like Copper Foil; Anticathode material of the present invention does not limit; Identical with prior art; Said negative material generally comprises negative electrode active material, binding agent and conductive agent, and said negative electrode active material can adopt all negative electrode active materials that are purchased, like graphite and/or lithium titanium oxygen compound.Said conductive agent can be in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more; Said binding agent can be one or more in Kynoar (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) and the butadiene-styrene rubber (SBR).The preparation method of said negative pole is similar with anodal preparation method, is not described in detail in this.
In the lithium ion battery of the present invention, electrolyte adopts the conventional nonaqueous electrolytic solution in this area.Electrolyte lithium salt can be selected from lithium hexafluoro phosphate (LiPF in the said electrolyte
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 said nonaqueous electrolytic solution, the concentration of electrolyte lithium salt can be 0.1-2mol/L.
According to the preparation method of lithium ion battery provided by the invention, except said positive pole prepared according to method provided by the invention, other steps were conventionally known to one of skill in the art.In general, this method comprises anodal, negative pole and the barrier film that is positioned at the positive and negative interpolar formation pole piece of reeling successively, and pole piece is inserted in the battery case, adds electrolyte, seals then, can obtain lithium ion battery provided by the invention.The method for winding of the barrier film between positive pole and negative pole is conventionally known to one of skill in the art, repeats no more at this.
Come to describe in more detail the present invention through embodiment below.
Embodiment 1
4ml 3-carboxy pyrrole is added the there-necked flask that 150mL distilled water is housed; Under mechanical agitation; By the ratio of 3-carboxy pyrrole and the amount of six hydration p-methyl benzenesulfonic acid iron substances is to drip p-methyl benzenesulfonic acid ferrous solution as oxidant and dopant at 1: 1, and at 0 ℃ of polymerization 6h, the powder that filtration is obtained respectively washs 3 times with distilled water, absolute alcohol under the Ar gas shiled; At 60 ℃ of vacuumize 24h, gathered (3-carboxyl) pyrroles's powder.
Embodiment 2
Six hydration p-methyl benzenesulfonic acid iron with 134g under the room temperature join in the 1mol/LHCl solution, stir, and 68.6g 2-sulfoacid aniline is joined in the above-mentioned solution; Sustained response 6h; Leave standstill, suction filtration, the powder that filtration is obtained respectively washs 3 times with distilled water, absolute alcohol; At 60 ℃ of vacuumize 24h, gathered (2-sulfonic acid) aniline powder.
Embodiment 3
With anhydrous FeCl
3Join in the there-necked flask that contains the 100mL chloroform, stir about 30min obtains the muddy liquid of dirty-green, will contain in the dropwise adding system of 50ml chloroformic solution of 0.12mol (3, the 4-dimethoxy) thiophene FeCl then
3With the ratio of the amount of substance of (3, the 4-dimethoxy) thiophene be 1: 1, sustained response 6h leaves standstill, the product that filtration is obtained respectively washs 3 times with distilled water, absolute alcohol,, is gathered (3, the 4-dimethoxy) thiophene powder at 60 ℃ of vacuumize 24h.
Embodiment 4
Anodal: as 9g PVDF binding agent and 3g to be gathered (3-carboxyl) pyrroles (embodiment 1 makes) and join among the NMP, after treating all to dissolve, 6g granule carbon black Super P conductive agent slowly is added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole: with Delanium, Super P conductive agent, binding agent SBR and CMC according to weight ratio 100: 2: 6: 2 evenly mix in deionized water.Be two-sided dressing on 10 microns the Copper Foil at thickness, smear evenly.120 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 491cm (length) * 45cm (wide) * 0.0086 (thick), and negative material weighs 2.14 grams.
Barrier film: PP/PE/PP trilamellar membrane (1090 ± 3) mm * 47mm * 0.018mm.
With above-mentioned positive and negative plate and square lithium-ion electric core of membrane coil coiled and be received in the rectangular cell shell, inject 1mol/L LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 0.5) electrolyte, lithium ion battery 1 is processed in sealing.
Embodiment 5
Anodal: as 7g PVDF binding agent and 3g to be gathered (2-sulfonic acid) aniline (embodiment 2 makes) and join among the NMP, after treating all to dissolve, 5g Super P conductive agent slowly is added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery 2.
Embodiment 6
Anodal: as 9g PVDF binding agent and 3g to be gathered (3, the 4-dimethoxy) thiophene (embodiment 3 makes) and join among the NMP, after treating all to dissolve, 6g Super P conductive agent slowly is added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery 3.
Embodiment 7
Anodal: as 6g PVDF binding agent and 6g to be gathered (3-carboxyl) pyrroles (embodiment 1 makes) and join among the NMP, after treating all to dissolve, 3g Super P conductive agent slowly is added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery 4.
Embodiment 8
Anodal: as 9g to be gathered (3-carboxyl) pyrroles (embodiment 1 makes) and join among the NMP, after treating all to dissolve, 3g Super P conductive agent slowly is added into wherein until being uniformly dispersed, then with 150gLiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery 5.
Comparative Examples 1
Anodal: as 9g PVDF binding agent to be joined among the NMP, after treating all to dissolve, 9g Super P conductive agent slowly is added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery C1.
Comparative Examples 2
Anodal: as 9g PVDF binding agent to be joined among the NMP, after treating all to dissolve, 3g polypyrrole and 6g Super P conductive agent slowly are added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery C2.
Comparative Examples 3
Anodal: as 7g PVDF binding agent and 3g polyaniline to be joined among the NMP, after treating all to dissolve, 5g Super P conductive agent slowly is added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery C3.
Comparative Examples 4
Anodal: as 9g PVDF binding agent to be joined among the NMP, after treating all to dissolve, 3g polythiophene and 6g Super P conductive agent slowly are added into wherein until being uniformly dispersed, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, and high-speed stirred was disperseed 2 hours, made anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery C4.
Comparative Examples 5
Anodal: as 9g to be gathered (3-carboxyl) pyrroles join among the NMP, after treating all to dissolve, then with 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in the above-mentioned mixed solution, disperses 2 hours in high-speed stirred, makes anode sizing agent.Be two-sided dressing on 16 microns the aluminium foil at thickness, smear evenly.140 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), contains 4.63 gram positive active materials.
Negative pole, diaphragm material are selected, the preparation method is all identical with embodiment 4, and according to embodiment 4 methods assembling lithium ion battery C5.
Battery performance test
The charge/discharge capacity of lithium ion battery 1-5, C1-C5 and cycle performance adopt method 1 and 2 respectively, and the result is as shown in table 1; The consistency assessment employing method 3 of cell, the result is as shown in table 2.
1, first charge-discharge test: prepared lithium ion battery is through constant voltage charge, and the restriction electric current is 0.2C, and final voltage is 3.6 volts; Discharge with the constant-current discharge mode, discharging current is 0.2C, and the cut-ff voltage of discharge is 2.0 volts, and is recorded in the discharge voltage of the mid point of discharge curve.
2, loop test: under 25 ℃ of conditions, with battery respectively with the 1C current charges to 3.6V, with constant-potential charge, cut-off current is 0.03C after voltage rises to 3.6V, shelves 10 minutes; Battery, was shelved 10 minutes to 2.0V with the 1C current discharge.Repeat above step 500 time.
Presented higher holdup=(the 500th cyclic discharge capacity/cyclic discharge capacity) first * 100%
3, cell uniformity test: above-mentioned lithium ion battery 1, C1, C2 are respectively made 10, the discharge capacity when writing down partial volume respectively (mAh/g), middle threshold voltage (V) and internal resistance (m Ω).
The partial volume process is following:
(1) constant-current discharge: electric current 0.2C, 360min, lower voltage limit 2.00V
(2) constant-current constant-voltage charging: electric current 0.2C, 480min, upper voltage limit 3.60V, cut-off current 10mA
(3) constant-current discharge: electric current 0.2C, 480min, lower voltage limit 2.00V
Table 1 Comprehensive Experiment tables of data
Table 2 partial volume tables of data
Can obtain from table 1, owing to added conducting polymer polypyrrole, polyaniline and polythiophene respectively, battery C2, C3 and C4 are with respect to the battery C1 that does not add conducting polymer, and the constant current charge and discharge specific capacity of battery, discharge voltage all increase; Battery 1,2 and 3 is respectively with respect to battery C2, C3 and C4; The conducting polymer that adds has polar group carboxyl, sulfonic group and alkoxyl respectively; The constant current charge-discharge specific capacity of battery, discharge voltage further improve, battery through the charge and discharge that repeatedly circulate after the conservation rate of capacity promote to some extent; Battery 5 has added granule carbon black SuperP conductive agent with respect to battery C5, and battery is obviously excellent through the capability retention behind the cycle charge-discharge repeatedly.Explain that the conducting polymer and the positive active material that contain polar group have stronger physical action; Serve as the conduction fulcrum and be connected lead; Serve as conductive node with the second close conductive agent of anodal utmost point active material particle diameter, in electrode, form effective conductive network, reduced the internal resistance of cell.
Can obtain from table 2, add the lithium ion battery 1 of the conducting polymer that has polar group, the discharge capacity maximum difference is that 0.3mAh/g, middle threshold voltage maximum difference 0.02V and internal resistance of cell maximum difference are 3m Ω between each battery; Be significantly less than the lithium ion battery C1 that does not add conducting polymer, the discharge capacity maximum difference is that 9.9mAh/g, middle threshold voltage maximum difference 0.14V and internal resistance of cell maximum difference are 8m Ω between each battery; Be lower than adding not with the lithium ion battery C2 of the conducting polymer of polar group, the discharge capacity maximum difference is that 2.2mAh/g, middle threshold voltage maximum difference 0.05V and internal resistance of cell maximum difference are 5m Ω between each battery.Polar functionalities is added in explanation in cell positive material conducting polymer can improve the consistency of battery.Through data set in the table 2 (1) lithium ion battery 2, C3 and C1; (2) discharge capacity maximum difference, middle threshold voltage maximum difference and internal resistance of cell maximum difference between each battery among lithium ion battery 3, C4 and the C1 also can draw the consistency that the conducting polymer that in cell positive material, adds polar functionalities can improve battery.
Claims (8)
1. anode material for lithium-ion batteries; This positive electrode contains positive active material and conductive agent; It is characterized in that; Said conductive agent comprises first conductive agent and second conductive agent, and said first conductive agent is the conducting polymer that contains polar group, and said second conductive agent is one or more in carbon black, graphite, carbon fiber, CNT, carbonyl nickel powder, copper powder, iron powder, zinc powder and the aluminium powder.
2. positive electrode according to claim 1, wherein, with respect to the said positive active material of 100 weight portions, the said content that contains the conducting polymer of polar group is 0.1～20 weight portion; The content of said second conductive agent is 0.1～20 weight portion.
3. positive electrode according to claim 1; Wherein, the said conducting polymer that contains polar group be polyaniline, the polypyrrole that contains polar group, the polythiophene that contains polar group that contain polar group, contain polar group gather furans, contain polar group polyhenylene, contain polar group coalescence benzene, contain polar group the p-phenylene vinylene, contain the polyacrylonitrile of polar group and contain in the metacetaldehyde of polar group one or more.
4. according to any described positive electrode among the claim 1-3, wherein, said polar group is one or more in carboxyl, hydroxyl, amino, halogen, nitro, alkoxyl, carbonyl, ester group, amide groups, sulfonic group, the organic salt.
5. positive electrode according to claim 1 and 2, wherein, said positive active material is LiCoO
2, LiMn
2O
4, LiNiO
2, LiVPO
4, LiCoAlO
2, LiMnCoO
2, LiFe
aM
1-aPO
4, LiCo
xNi
yMn
zO
2In one or more, wherein M is one or more among Co, Ni and the Mn, 0.8≤a≤1; X+y+z=1,0≤x≤1,0≤y≤1,0≤z≤1.
6. positive electrode according to claim 1 and 2, wherein, this positive electrode also contains binding agent, and with respect to the said positive active material of 100 weight portions, the content of said binding agent is 1～20 weight portion.
7. positive electrode according to claim 6; Wherein, said binding agent be Kynoar, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, butadiene-styrene rubber, gather methylcellulose, gather sodium carboxymethylcellulose pyce, in hydroxypropyl methylcellulose and the POLYPROPYLENE GLYCOL one or more.
8. lithium ion battery; This lithium ion battery comprises battery case, pole piece and electrolyte; Said pole piece and electrolyte are sealed in the battery case; Said pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that, contained positive electrode is any said anode material for lithium-ion batteries among the claim 1-7 in the said positive pole.
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