CN102487141B - Cathode material of lithium ion battery and battery - Google Patents
Cathode material of lithium ion battery and battery Download PDFInfo
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- CN102487141B CN102487141B CN201010578915.2A CN201010578915A CN102487141B CN 102487141 B CN102487141 B CN 102487141B CN 201010578915 A CN201010578915 A CN 201010578915A CN 102487141 B CN102487141 B CN 102487141B
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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 the battery of a kind of anode material for lithium-ion batteries and this positive electrode of use.
Background technology
Lithium ion battery has the advantages that discharge voltage is high, energy density is high and service life cycle is long, therefore in field of portable electronic devices, is used widely, and is subject to as the favor in some high-tech application fields such as military affairs, space flight, electric automobile simultaneously.
Lithium ion battery main performance index has battery capacity and cycle performance, and the quality of battery performance depends on electrode material.Tradition lithium battery is comprised of positive pole, negative pole, barrier film and electrolyte.Anode material for lithium-ion batteries contains positive active material, conductive agent and binding agent.In tradition lithium ion cell electrode preparation process, add the conductive agents such as a certain amount of carbon black, graphite, and add the binding agents such as a certain amount of Kynoar, polytetrafluoroethylene.Add the more conductive agent of insulating properties binding agent needs for battery discharge, and add the conductive agent of high-specific surface area to require more binding agent to carry out machine-shaping.Described conductive agent and binding agent do not possess electro-chemical activity, thereby cause the relative amount of electroactive substance in electrode lower, affected the actual specific capacity of electrode integral, and its content in electrode and the deployment conditions high power discharge performance that can affect battery.
There are some researches show, to adding after chemistry or electrochemical doping the conducting polymer containing pi-electron conjugated structure that can be changed to conductor or semiconductor by insulator in electrode material, as contain polypyrrole, polyaniline, polythiophene, the poly-isostructural polymer of furans, can improve the translational speed of electronics and lithium ion in 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, described 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 described lithium rechargeable battery has higher battery capacity and better cycle performance.
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 applying is in uneven thickness, cause the batch battery consistency of preparation poor, and existing a large amount of electric tool such as electric motor car etc. all adopt a large amount of battery series-parallel connections that electric power is provided, the properties of battery pack is absolutely not the algebraic addition of single battery performance.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 large person of capacity always fill the shallow state of putting in little electric current is shallow, and the little person of capacity is always in large electric current super-charge super-discharge state, performance parameter difference is increasing between the two, and low capacity person lost efficacy in advance; Or make the series resistance that becomes power consumption that internal resistance is large, and it is too high easily to generate heat, and shortens the life-span.In the use procedure of battery pack, the temperature of each battery unit, voltage, electric current etc. are different, and after work a period of time, the consistency of battery pack continues to worsen certainly, finally cause the efficiency of battery to be reduced to rapidly the level that cannot accept and continue use.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 preparing 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 invention provides a kind of anode material for lithium-ion batteries, this positive electrode contains positive active material and conductive agent, wherein, described conductive agent comprises the first conductive agent and the second conductive agent, described the first conductive agent is the conducting polymer that contains polar group, and described the second conductive agent is one or more in carbon black, graphite, carbon fiber, carbon nano-tube, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder.
The present invention also provides a kind of lithium ion battery, this lithium ion battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte are sealed in battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, in described positive pole, contained positive electrode is anode material for lithium-ion batteries provided by the invention.
In positive electrode provided by the invention, contain the conducting polymer that the first conductive agent contains polar group, in slurry preparation process, polar group is conducive to form hydrogen bond with the second conductive agent and positive active material surface, strengthen their degrees of scatter in solvent, slurry is more easily applied, coating thickness is even, the pole piece high conformity of preparation.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 internal resistance is all better than not adding conducting polymer and adds the battery that conducting polymer of polar functionalities is not made.
In addition, the conducting polymer of polar functionalities can Substitute For Partial binding agent and conductive agent, reduce electrochemistry inert component in battery, and the conducting polymer that contains polar group and positive active material have stronger physical action, serve as conduction fulcrum and be connected wire, the second conductive agent serves as conductive node (particularly in the situation that the particle diameter of the particle diameter of the second conductive agent and anodal utmost point active material is close), in electrode, form effective conductive network, reduced the internal resistance of cell, thereby the battery of preparation have height ratio capacity and excellent cycle performance.As embodiment 4 is respectively 123.0mAh/g, 114.4mAh/g, 118.0mAh/g with the specific capacity of comparative example 1,2 obtained lithium ion batteries; Cell voltage discharge platform is respectively 3.39V, 3.15V, 3.26V; The capability retention after 500 times that circulates is respectively 92.2%, 91.2%, 91.4%.Contain the lithium ion battery with the conducting polymer of polar group, with respect to the lithium ion battery that does not contain conducting polymer or contain the conducting polymer of not being with polar group, its battery specific capacity, discharge voltage and the rear capability retention that repeatedly circulates are improved.
Embodiment
Anode material for lithium-ion batteries provided by the invention contains positive active material and conductive agent, wherein, described conductive agent comprises the first conductive agent and the second conductive agent, described the first conductive agent is the conducting polymer that contains polar group, and described the second conductive agent is one or more in carbon black, graphite, carbon fiber, carbon nano-tube, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder.
With respect to the positive active material of 100 weight portions, described in contain polar group the content of conducting polymer can be 0.1～20 weight portion, be preferably 0.5～10 weight portion.
The described conducting polymer that contains polar group can be one or more of the polyaniline that contains polar group, the polypyrrole that contains polar group, the polythiophene that contains polar group, the poly-furans that contains polar group, the polyhenylene (poly-to benzene) that contains polar group, the coalescence benzene that contains polar group, the p-phenylene vinylene of containing polar group, the polypropylene that contains polar group and the metacetaldehyde that contains polar group.Described polar group can be arranged in main chain and/or the side chain of described conducting polymer.Described polar group can be 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
21straight or branched alkyl), (CO-R, wherein R is preferably C to carbonyl
2-C
21straight or branched alkyl), ester group (O-CO-R or-CO-O-R, wherein R is preferably C
2-C
21straight or branched alkyl), amide groups (CO-NH-R or-NH-CO-R, wherein R is preferably C
2-C
21straight or branched alkyl), one or more in sulfonic group and organic salt.Described organic salt can be carboxylate, ammonium salt, sulfonate, phosphate etc.The described conducting polymer that contains polar group can be by the monomer polymerization of the conducting polymer that contains polar group is obtained, and the method for polymerization and condition can be identical with the polymerization process of the monomer of the conducting polymer of polar functionalities not.
In the present invention, described the second conductive agent can be one or more in carbon black, graphite, carbon fiber, carbon nano-tube, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder.With respect to the positive active material of 100 weight portions, the content of the second conductive agent can be 0.1～20 weight portion, is preferably 0.5～10 weight portion.
Described positive active material can, for the various positive active materials for lithium ion battery of this area routine, be preferably LiCoO
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
2one or more in (x+y+z=1,0≤x≤1,0≤y≤1,0≤z≤1).
Described positive electrode can also contain binding agent, binding agent can be the various anodal binding agents for lithium ion battery of this area routine, is preferably one or more in Kynoar, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, butadiene-styrene rubber, poly-methylcellulose, poly-sodium carboxymethylcellulose pyce, hydroxypropyl methylcellulose and POLYPROPYLENE GLYCOL.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 the conventional the whole bag of tricks in this area, for example with solvent, positive active material, binding agent and conductive agent are prepared into positive electrode slurries, the addition of solvent is conventionally known to one of skill in the art, can adjust according to the viscosity of the slurry coating of anodal slurries and the requirement of operability.Then made positive electrode slurries slurry is coated in the upper dry compressing tablet of collector (can use any collector body known in the field, for example aluminium foil), then cut-parts form lithium ion cell positive.Described dry temperature range of choice can be 90～150 ℃, can be 10～40min drying time.
Described solvent can be various solvents known in the field, be preferably water, 1-METHYLPYRROLIDONE (NMP), N, one or more in dinethylformamide (DMF), N, N-dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), 1,2-PD carbonic ester, alcohol, oxolane and acetone.
Negative pole in lithium ion battery of the present invention can be various negative poles known in the field.Described negative pole contains the negative material in collector and coated collector, and described collector can adopt the various collectors for lithium ion battery in prior art, as Copper Foil; Anticathode material of the present invention is not restricted, same as the prior art, described negative material generally comprises negative electrode active material, binding agent and conductive agent, and described negative electrode active material can adopt all negative electrode active materials that are purchased, as graphite and/or lithium titanium oxygen compound.Described conductive agent can be one or more in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, silicon alloy; Described binding agent can be one or more in Kynoar (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR).The preparation method of described negative pole and anodal preparation method are similar, are not described in detail in this.
In lithium ion battery of the present invention, electrolyte adopts the nonaqueous electrolytic solution of this area routine.In described electrolyte, electrolyte lithium salt can be selected from lithium hexafluoro phosphate (LiPF
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 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, and wherein chain acid esters can be for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other is fluorine-containing, sulfur-bearing or containing one or more in the chain organosilane ester of unsaturated bond.Ring-type acid esters can be for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other is fluorine-containing, sulfur-bearing or containing one or more in the ring-type organosilane ester of unsaturated bond.In described 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 described positive pole is according to method preparation provided by the invention, other steps are conventionally known to one of skill in the art.In general, the method comprises anodal, negative pole and the barrier film that the is positioned at positive and negative interpolar formation pole piece of reeling successively, and pole piece is inserted in battery case, adds electrolyte, then seals, and 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, does not repeat them here.
Below by embodiment, the present invention is described in more detail.
Embodiment 1
4ml 3-carboxy pyrrole is added to the there-necked flask that 150mL distilled water is housed; under mechanical agitation; by 3-carboxy pyrrole, be to drip p-methyl benzenesulfonic acid ferrous solution at 1: 1 as oxidant and dopant with the ratio of the amount of six hydration p-methyl benzenesulfonic acid iron substances; under Ar gas protection at 0 ℃ of polymerization 6h; distilled water, absolute alcohol for powder that filtration is obtained respectively wash 3 times; at 60 ℃ of vacuumize 24h, gathered (3-carboxyl) pyrroles's powder.
Embodiment 2
Under room temperature, the six hydration p-methyl benzenesulfonic acid iron of 134g are joined in 1mol/LHCl solution, stir, 68.6g 2-sulfoacid aniline is joined in above-mentioned solution, sustained response 6h, standing, suction filtration, distilled water, absolute alcohol for powder that filtration is obtained respectively wash 3 times, at 60 ℃ of vacuumize 24h, gathered (2-sulfonic acid) aniline powder.
Embodiment 3
By anhydrous FeCl
3join containing in the there-necked flask of 100mL chloroform, stir about 30min, obtains dirty-green dirty solution, then will dropwise add in system containing the 50ml chloroformic solution of 0.12mol (3,4-dimethoxy) thiophene FeCl
3with the ratio of the amount of substance of (3,4-dimethoxy) thiophene be 1: 1, sustained response 6h, standing, distilled water, absolute alcohol for product that filtration is obtained respectively wash 3 times, at 60 ℃ of vacuumize 24h, are gathered (3,4-dimethoxy) thiophene powder.
Embodiment 4
Anodal: 9g PVDF binding agent and poly-(3-carboxyl) pyrroles (embodiment 1 makes) of 3g to be joined in NMP, after all dissolving, 6g granule carbon black Super P conductive agent is slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.140 ℃ of oven dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole: by Delanium, Super P conductive agent, binding agent SBR and CMC according to weight ratio 100: 2: 6: 2 evenly mix in deionized water.At thickness, be two-sided dressing on the Copper Foil of 10 microns, smear evenly.At 120 ℃, dry, roll, rolling cut becomes positive plate, and 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.
Above-mentioned positive and negative plate and membrane coil are coiled into a square lithium-ion electric core and are received in rectangular cell shell, inject subsequently 1mol/L LiPF
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 0.5) electrolyte, sealing, makes lithium ion battery 1.
Embodiment 5
Anodal: 7g PVDF binding agent and poly-(2-sulfonic acid) aniline (embodiment 2 makes) of 3g to be joined in NMP, after all dissolving, 5g Super P conductive agent is slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion batteries 2.
Embodiment 6
Anodal: 9g PVDF binding agent and poly-(3, the 4-dimethoxy) thiophene (embodiment 3 makes) of 3g to be joined in NMP, after all dissolving, 6g Super P conductive agent is slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion batteries 3.
Embodiment 7
Anodal: 6g PVDF binding agent and poly-(3-carboxyl) pyrroles (embodiment 1 makes) of 6g to be joined in NMP, after all dissolving, 3g Super P conductive agent is slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion batteries 4.
Embodiment 8
Anodal: poly-(3-carboxyl) pyrroles (embodiment 1 makes) of 9g to be joined in NMP, after all dissolving, 3g Super P conductive agent is slowly added into wherein until be uniformly dispersed, then by 150gLiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion batteries 5.
Comparative example 1
Anodal: 9g PVDF binding agent to be joined in NMP, after all dissolving, 9g Super P conductive agent is slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion battery C1.
Comparative example 2
Anodal: 9g PVDF binding agent to be joined in NMP, after all dissolving, 3g polypyrrole and 6g Super P conductive agent are slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion battery C2.
Comparative example 3
Anodal: 7g PVDF binding agent and 3g polyaniline to be joined in NMP, after all dissolving, 5g Super P conductive agent is slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion battery C3.
Comparative example 4
Anodal: 9g PVDF binding agent to be joined in NMP, after all dissolving, 3g polythiophene and 6g Super P conductive agent are slowly added into wherein until be uniformly dispersed, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion battery C4.
Comparative example 5
Anodal: poly-(3-carboxyl) pyrroles of 9g to be joined in NMP, after all dissolving, then by 150g LiFePO
4/ C (carbon content 2.32%) powder slowly joins in above-mentioned mixed solution, in high-speed stirred, disperses 2 hours, makes anode sizing agent.At thickness, be two-sided dressing on the aluminium foil of 16 microns, smear evenly.At 140 ℃, dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) * 44cm (wide) * 0.0138cm (thick), containing 4.63 grams of positive active materials.
Negative pole, diaphragm material are selected, preparation method is all identical with embodiment 4, and according to embodiment 4 method assembling lithium ion battery C5.
Battery performance test
The charge/discharge capacity of lithium ion battery 1-5, C1-C5 and cycle performance adopt respectively method 1 and 2, and result is as shown in table 1; The compliance evaluation employing method 3 of cell, result is as shown in table 2.
1, first charge-discharge test: prepared lithium ion battery is by constant voltage charge, and Limited Current is 0.2C, and final voltage is 3.6 volts; In constant-current discharge mode, discharge, discharging current is 0.2C, and the cut-ff voltage of electric 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, by battery respectively with 1C current charges to 3.6V, after voltage rises to 3.6V, with constant-potential charge, cut-off current is 0.03C, shelves 10 minutes; Battery, is shelved 10 minutes to 2.0V with 1C current discharge.Repeat above step 500 time.
Capacity dimension holdup=(the 500th cyclic discharge capacity/first cyclic discharge capacity) * 100%
3, cell uniformity test: above-mentioned lithium ion battery 1, C1, C2 are respectively made to 10, the discharge capacity while recording partial volume respectively (mAh/g), middle threshold voltage (V) and internal resistance (m Ω).
Partial volume process is as follows:
(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
From table 1, can obtain, owing to having added respectively conducting polymer polypyrrole, polyaniline and polythiophene, 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 adding is respectively with polar group carboxyl, sulfonic group and alkoxyl, the constant current charge-discharge specific capacity of battery, discharge voltage further improve, and the conservation rate of battery capacity after the charge and discharge that repeatedly circulate promotes to some extent; Battery 5, with respect to battery C5, has added granule carbon black SuperP conductive agent, and battery is obviously excellent through the capability retention after cycle charge-discharge repeatedly.Illustrate that the conducting polymer and the positive active material that contain polar group have stronger physical action, serve as conduction fulcrum and be connected wire, second conductive agent close with anodal utmost point active material particle diameter serves as conductive node, forms effective conductive network in electrode, reduced the internal resistance of cell.
From table 2, can obtain, add the lithium ion battery 1 with the conducting polymer of polar group, between each battery, 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; Be significantly less than the lithium ion battery C1 that does not add conducting polymer, between each battery, 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; Lower than the lithium ion battery C2 that adds the conducting polymer of not being with polar group, between each battery, 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.The conducting polymer that polar functionalities is added in explanation in cell positive material can improve the consistency of battery.By data group (1) lithium ion battery 2, C3 and C1 in table 2; (2) discharge capacity maximum difference, middle threshold voltage maximum difference and internal resistance of cell maximum difference between each battery in lithium ion battery 3, C4 and C1, also can show that the conducting polymer that adds polar functionalities in cell positive material can improve the consistency of battery.
Claims (7)
1. an anode material for lithium-ion batteries, this positive electrode contains positive active material and conductive agent, it is characterized in that, described conductive agent comprises the first conductive agent and the second conductive agent, described the first conductive agent is the conducting polymer that contains polar group, and described the second conductive agent is one or more in carbon black, graphite, carbon fiber, carbon nano-tube, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder;
Wherein, with respect to the described positive active material of 100 weight portions, described in contain polar group the content of conducting polymer be 0.1～20 weight portion; The content of described the second conductive agent is 0.1～20 weight portion.
2. positive electrode according to claim 1, wherein, the conducting polymer that contains polar group described in is one or more in the polyaniline that contains polar group, the polypyrrole that contains polar group, the polythiophene that contains polar group, the poly-furans that contains polar group, the polyhenylene that contains polar group, the coalescence benzene that contains polar group, the p-phenylene vinylene of containing polar group, the polyacrylonitrile that contains polar group and the metacetaldehyde that contains polar group.
3. positive electrode according to claim 1 and 2, wherein, described polar group is one or more in carboxyl, hydroxyl, amino, halogen, nitro, alkoxyl, carbonyl, ester group, amide groups, sulfonic group, organic salt.
4. positive electrode according to claim 1, wherein, described 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 in Co, Ni and Mn, 0.8≤a≤1; X+y+z=1,0≤x≤1,0≤y≤1,0≤z≤1.
5. positive electrode according to claim 1, wherein, this positive electrode also contains binding agent, and with respect to the described positive active material of 100 weight portions, the content of described binding agent is 1～20 weight portion.
6. positive electrode according to claim 5, wherein, described binding agent is one or more in Kynoar, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy resin, butadiene-styrene rubber, poly-methylcellulose, poly-sodium carboxymethylcellulose pyce, hydroxypropyl methylcellulose and POLYPROPYLENE GLYCOL.
7. a lithium ion battery, this lithium ion battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte are sealed in battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that, in described positive pole, contained positive electrode is anode material for lithium-ion batteries described in any one in claim 1-6.
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102779983B (en) * | 2012-08-15 | 2014-06-04 | 泉州劲鑫电子有限公司 | Production method for positive pole of high-power nickel-metal hydride battery |
| CN106159214B (en) * | 2015-03-31 | 2019-09-13 | 比亚迪股份有限公司 | Electrode slurry presoma, electrode slurry and preparation method thereof, electrode and lithium ion battery |
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| CN108232198A (en) * | 2017-12-29 | 2018-06-29 | 东莞力朗电池科技有限公司 | A kind of lithium ion battery |
| EP3785312A4 (en) * | 2018-04-27 | 2021-12-15 | Dow Global Technologies Llc | Solvent systems for use in lithium ion battery production |
| CN110718674A (en) * | 2019-10-15 | 2020-01-21 | 宁波铵特姆新能源科技有限公司 | Current collector conductive coating and preparation method thereof |
| CN112563511B (en) * | 2020-12-10 | 2022-03-04 | 深圳中科瑞能实业有限公司 | Aluminum-containing negative electrode material, negative electrode plate and lithium ion secondary battery |
| CN112563528A (en) * | 2020-12-15 | 2021-03-26 | 广东国鸿氢能科技有限公司 | Preparation method of compression molding bipolar plate |
| CN113013414B (en) * | 2021-02-26 | 2023-02-24 | 蜂巢能源科技有限公司 | Cobalt-free positive electrode slurry, preparation method thereof, positive plate and lithium ion battery |
| CN113314704B (en) * | 2021-05-28 | 2023-06-30 | 赣州市沃能新能源有限公司 | Lithium halide high-energy-density battery positive electrode slurry and preparation method thereof |
| CN115770879A (en) * | 2022-12-01 | 2023-03-10 | 上海我赛电池科技有限公司 | Solid state battery coating roll |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1423353A (en) * | 2001-09-05 | 2003-06-11 | 三星Sdi株式会社 | Active material for cell and preparing method |
| CN101630728A (en) * | 2009-04-16 | 2010-01-20 | 华中科技大学 | High energy density lithium secondary battery electrode and preparation method thereof |
| CN101651233A (en) * | 2008-08-14 | 2010-02-17 | 比亚迪股份有限公司 | Lithium ion secondary battery and preparation method thereof |
| CN101867037A (en) * | 2010-06-23 | 2010-10-20 | 深圳清华大学研究院 | Iron-phosphate-based lithium-ion battery positive plate and preparation method thereof |
-
2010
- 2010-12-02 CN CN201010578915.2A patent/CN102487141B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1423353A (en) * | 2001-09-05 | 2003-06-11 | 三星Sdi株式会社 | Active material for cell and preparing method |
| CN101651233A (en) * | 2008-08-14 | 2010-02-17 | 比亚迪股份有限公司 | Lithium ion secondary battery and preparation method thereof |
| CN101630728A (en) * | 2009-04-16 | 2010-01-20 | 华中科技大学 | High energy density lithium secondary battery electrode and preparation method thereof |
| CN101867037A (en) * | 2010-06-23 | 2010-10-20 | 深圳清华大学研究院 | Iron-phosphate-based lithium-ion battery positive plate and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| Effect of binary conductive agents in LiCoO2 cathode on performances of lithium ion polymer battery;S.E.Cheon,et al.;《Electrochimica Acta》;20000616;全文 * |
| Flexible,Aligned Carbon Nanotube/Conducting Polymer Electrodes for a Lithium-Ion Battery;Jun Chen,et al.;《Chem.Mater.》;20070329;全文 * |
| JunChen et al..Flexible |
| S.E.Cheon,et al..Effect of binary conductive agents in LiCoO2 cathode on performances of lithium ion polymer battery.《Electrochimica Acta》.2000,全文. |
| 许晶玮等.高分子/石墨复合材料的制备与导电性能的研究进展.《化学通报》.2007,全文. |
| 高分子/石墨复合材料的制备与导电性能的研究进展;许晶玮等;《化学通报》;20070831;全文 * |
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