CN1316653C - Positive electrode material for lithium ion cell, its preparing method and lithium ion cell - Google Patents

Positive electrode material for lithium ion cell, its preparing method and lithium ion cell Download PDF

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CN1316653C
CN1316653C CNB2005100202729A CN200510020272A CN1316653C CN 1316653 C CN1316653 C CN 1316653C CN B2005100202729 A CNB2005100202729 A CN B2005100202729A CN 200510020272 A CN200510020272 A CN 200510020272A CN 1316653 C CN1316653 C CN 1316653C
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polymer
lithium
lithium ion
group
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CN1652376A (en
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邓正华
胡国和
王小兵
王璐
陈勉忠
张晓正
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Sichuan Indigo Technology Co.,Ltd.
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Chengdu Organic Chemicals Co Ltd of CAS
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

Abstract

The present invention relates to a positive electrode material for a lithium ion cell, a preparing method thereof and the lithium ion cell. The positive electrode material for a lithium ion cell relates to a LiMn2O4 electrode piece trimmed and treated by a functional polymer, which is formed by that a LiMn2O4 electrode piece is trimmed by a polymer containing a functional group having complexation capability with Mn ion. The LiMn2O4 electrode piece trimmed by a functional polymer overcomes the problems that fine particles are difficult to clad and secondary pulverizing is easy to result in cladding layer dropping in oxide cladding and trimming the LiMn2O4 material with a conductive polymer material. Due to the complexation and valence bond functions of the polar group of the polymer and the Mn ion at the surface of LiMn2O4 particles, the oxidative decomposition ability of Mn<4+> ion to electrolytic liquid and disproportionation degree of Mn<3+> ion are reduced, the dissolution and migration of lithium ion is prevented, and thereby, the high-temperature cyclical stability of the lithium ion battery adopting the LiMn2O4 as the positive electrode is enhanced. The positive electrode material for a lithium ion cell of the present invention has the advantage of simple and feasible preparing process, and has better industrial production value.

Description

A kind of anode material for lithium-ion batteries, its preparation method and lithium ion battery
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, exactly relate to a kind of manganate cathode material for lithium.
Background technology
In current informationalized society, chemical power source is subjected to people day by day and payes attention to widely, and wherein lithium ion battery is because operating voltage height, energy density are big, and environmental pollution is little and become the energy of numerous portable electric appts and power system of electric automobile.The earliest commercial lithium ion battery that is in the market most positive electrodes that adopt are LiCoO 2Because cobalt resource lacks, costs an arm and a leg, and harmful to environment, so urgent searching of people a kind ofly can replace LiCoO 2Positive electrode.Spinelle LiMn 2O 4Owing to have aboundresources, cheap, the environmentally friendly and synthetic advantage such as simple is the focus that people study always, is considered to the most promising positive electrode in the lithium ion battery, the particularly rise of electrokinetic cell, cheap spinelle LiMn 2O 4Have very big competitive advantage and huge application market.But spinelle LiMn 2O 4Cycle performance still can not reach real requirement so far, particularly at high temperature (〉=55 ℃) charge/discharge capacity decay serious [Yongyao Xia, Massaki Yoshio.Journal of Power Sources, 1997,66:129], this defective has hindered its application.
In recent years to LiMn 2O 4The research of high temperature charge/discharge capacity loss mechanism, people have following common recognition to this: the unsettled two phase structure of high pressure (4.15V) changes to stable phase structure, and with the loss of manganese oxide; Mn 2O 3Direct dissolving in electrolyte; The oxidation Decomposition of electrolyte on electrode.LiMn 2O 4The reason of the irreversible decay of capacity at high temperature can be regarded as temperature and raises, the Mn in the spinelle octahedron 3+Ion generation disproportionated reaction causes that the cation position randomness increases, and forms unordered spinel structure (MnLi 1-x) (Mn 2-xLi x) O 4, this process has been quickened the dissolving loss of Mn ion, and significantly the electrochemical oxidation of catalytic electrolysis liquid decomposes.The existence of hydrone produces the proton H of trace in electrolyte oxidation or the electrolyte +, H +With LiMn 2O 4Reaction has aggravated again the dissolving of manganese, LiMn when high temperature has been accelerated in this vicious circle 2O 4The decay of capacity has generated the protonated γ-MnO that does not have electro-chemical activity at last 2
In order to improve LiMn 2O 4High temperature circulation stability, the technology path that adopts in recent years is to LiMn 2O 4The oxide coating is carried out on the surface and conducting polymer materials is modified, and stops electrolyte and LiMn 2O 4Particle directly contacts, with the oxidation Decomposition of reduction electrolyte and the dissolving of manganese ion.Described oxide such as MgO, ZnO, Co 2O 3, LiAlO 2Deng, described conducting polymer materials such as polyaniline, polypyrrole, polythiophene etc.
The oxide method for coating is with the hydrogel of metal ion and LiMn 2O 4Mix to make presoma, sintering at high temperature makes the metal hydroxides Dehydration get the LiMn that oxide coats then 2O 4Conducting polymer modified LiMn 2O 4Method usually adopt conductive polymer solution that it is coated.For example, the polyaniline with eigenstate is dissolved in the 1-METHYLPYRROLIDONE solvent then LiMn 2O 4Add in this solution and stir, use again precipitating reagent the LiMn of polyaniline-coated 2O 4Separate, use after drying.The LiMn that coats like this 2O 4High temperature circulation is had a better role.
But still there is following point in such scheme: during (1) high temperature imitation frosted glass, target product easily produces caking, forms the coating of larger particles, has affected the operability of follow-up processing; (2) to LiMn 2O 4Thinner particle in the powder, little because of particle, surface energy is big, be difficult for being wrapped by, the homogeneity of target product is poor; (3) LiMn 2O 4The clad on surface carries out secondary processing process such as with slurry at target product, is coated with, rolls etc., and clad may be destroyed, and loses role that clad is answered; (4) LiMn 2O 4After coating, the gram volume of target product descends bigger, has increased again cost simultaneously; (5) conducting polymer is expensive, and the compositing conducting polymer process has bigger pollution to environment; Therefore, this technology path commercial-free is worth, and does not still have the report of suitability for industrialized production at present.
For this reason, be necessary to design a kind of new anode material for lithium-ion batteries, and prepare lithium ion battery with this positive electrode, reach and improve LiMn 2O 4The high temperature circulation stability purpose of battery.
Summary of the invention
Technical scheme of the present invention has provided a kind of anode material for lithium-ion batteries, and another technical scheme of the present invention has provided the preparation method of this positive electrode and the lithium ion battery that is prepared by this positive electrode.
Anode material for lithium-ion batteries provided by the invention is the LiMn that functional polymer is modified 2O 4Electrode slice, described functional polymer contain can with the functional group of Mn ion complexation.
Wherein, describedly can be with the functional group of Mn ion complexation :-CN ,-CON-,-CO-or-the COO-group.
Described functional polymer is to be formed by one or more polymerization of vinyl monomer, have at least in the described vinyl monomer a kind of containing-CN ,-CON-,-CO-or-the COO-group; Specifically described functional polymer can be a kind of homopolymers that contains the vinyl monomer of above-mentioned functional group; Or the two or more copolymers that contain the vinyl monomer of above-mentioned functional group; Or one or more vinyl monomers that contain above-mentioned functional group and the copolymer that does not contain the vinyl monomer of above-mentioned functional group, two kinds of monomer constitutive molar ratios are 1: 0.1～10.
Further, the vinyl monomer of described containing-CN group is: acrylonitrile, methacrylonitrile or inclined to one side dicyano ethene; Contain-vinyl monomer of CON-group is: acrylamide, acrylamide diacetone, the two propionitrile of acrylamide, acrylamide list propionitrile or methylene-bisacrylamide; Contain-vinyl monomer of CO-group is: N-vinyl pyrrolidone or general formula are CH 2=CH (CH 2) ketone of nCOR, n=0 wherein, 1,2,3......, R are all kinds of alkyl; Contain-vinyl monomer of COO-group is: anhydrides vinyl monomer or general formula are CH 2=CH (CH 2) the ester class vinyl monomer of nCOOR, wherein, n=0,1,2,3......., R are all kinds of alkyl; Describedly do not contain-CN ,-CON-,-CO-and-vinyl monomer of COO-group is: 4-vinylpridine, vinyl ethers, styrene or vinylacetate.
One of preparation method of anode material for lithium-ion batteries provided by the invention is: use the solution impregnation of functional polymer or apply LiMn 2O 4Electrode, the volatilization organic solvent obtains the LiMn that functional polymer is modified 2O 4
Specifically the preparation method is: with LiMn 2O 4Join in a kind of polypropylene copolymer aqueous binder of battery special use with conductive agent, use high-speed stirred to become finely dispersed slurry, then slurry is coated on the aluminium foil collector body, oven dry obtains LiMn 2O 4Electrode slice; To contain and to obtain functional polymer with the monomer of the functional group of Mn ion complexation ability by chemical polymerization, be mixed with then the polymer solution that mass percent concentration is 5-20%, again with this solution impregnation or apply LiMn 2O 4Electrode slice behind the solvent flashing, namely gets polymer-modified LiMn 2O 4Electrode slice.
Wherein, the solution of described functional polymer is the free radical polymerization method preparation by this area routine, 5～40 parts of weight are contained-CN or-CON-or-CO-and-vinyl monomer of COO-group two or more add in reactors, the solvent that adds 50～300 parts of weight again, stir, in adding monomer gross mass 1%～5% ratio adding initator, feeding nitrogen is removed the oxygen in the reaction system, its polymerization temperature is 45～80 ℃, polymerization reaction time 2～48 hours; Its reaction medium still is water-soluble corresponding various organic solvent or the distilled water (or deionized water) selected according to the oil-soluble of reaction monomers, polymerization initiator equally according to the oil-soluble of reaction medium and water-soluble select the oiliness initator (as azodiisobutyronitrile (AIBN), benzoyl peroxide (BPO) or water soluble starter (as ammonium persulfate, potassium peroxydisulfate etc.).With prepared polymer suction filtration, drying obtain containing can with the polymer of the functional group of Mn ion complexation ability, again polymer dissolution is obtained the solution of functional polymer in polar organic solvent.
Anode material for lithium-ion batteries provided by the invention can also be prepared by following methods: at preparation LiMn 2O 4Add during electrode contain-CN ,-CON-,-CO-and-vinyl monomer and the initator of COO-group, make the LiMn that contains polymerisable monomer 2O 4Electrode slice carried out thermal polymerization 2～8 hours with this electrode slice again or uses the UV-irradiation initiated polymerization to obtain the LiMn that functional polymer is modified under 60～150 ℃ temperature 2O 4Electrode slice.Described polymerization reaction is the radical polymerization of this area routine.
Wherein, the LiMn that contains polymerisable monomer 2O 4Electrode slice is at preparation LiMn 2O 4In time, add functional polymerization monomer wherein; Specifically: will contain and to join LiMn with monomer and the initator of the functional group of Mn ion complexation 2O 4, be mixed together in the slurry that forms of conductive agent and adhesive to be coated on the aluminium foil after stirring and obtain.The addition of monomer is LiMn 2O 41.0～5.0% of weight; Initator is AIBN, BPO etc., and the initator addition is 1.0～10.0% of monomer weight, adding mode: be dissolved in the monomer in advance at normal temperatures.
The LiMn that the present invention also provides functional polymer to modify 2O 4The lithium ion battery that electrode slice forms, it is with polymer-modified LiMn 2O 4Electrode is anodal, and take Delanium or native graphite as negative pole, polymer microporous film is battery isolating film, LiPF 6Organic solution consist of lithium ion battery as electrolyte.
Wherein, the making of artificial plumbago negative pole sheet is: it is in 5% the LA132 aqueous binder that 300 gram Delaniums are joined 300 gram concentration, and be uniformly dispersed with homogenizer and prevent into slurry, then slurry is coated on the Copper Foil, promptly get the artificial plumbago negative pole sheet behind the oven dry moisture.
The present invention utilization-CN ,-CON-,-CO-and-the COO-group is to LiMn 2O 4The Mn ion that plane of crystal is exposed produces complexing, has reduced the binding energy of Mn ion, reduces Mn 3+Ion generation disproportionated reaction degree stops the stripping and the migration of power manganese ion.In addition, LiMn 2O 4The exposed Mn ion of particle surface by complexing after, reduced Mn 4+The oxidative decomposition capacity of ion pair electrolyte improves with LiMn thereby reached 2O 4Purpose for the high temperature circulation stability of the lithium ion battery of positive pole.
Therefore, advantage of the present invention is:＜1〉overcome LiMn 2O 4After inorganic oxide and conducting polymer coating, the problem that causes gram volume to descend;＜2〉overcome LiMn 2O 4Fine grained coats difficult problem in the material;＜3〉there is not coating LiMn 2O 4Bonding and separating twice problem and to the impact of pole piece coating process;＜4〉polymer-filled LiMn 2O 4The packing of coating has been improved in the space of coating, can reduce the uptake of electrolyte, utilize polymer can with the complexing of Mn ion, reduce the oxidative decomposition of electrolyte, reduce the stripping of manganese ion, thereby improve the battery high-temperature cyclical stability;＜5〉implementing process of this technology is simple, has preferably industrialization value.
Description of drawings
Fig. 1 .LiMn 2O 4The electron binding energy spectrogram of manganese ion before and after the electrode modification.Abscissa is an electron binding energy, eV.Curve 1 is the LiMn of unmodified among the figure 2O 4In the electronic energy spectrum of Mn ion, the LiMn of curve 2 after for the functional polymer modification 2O 4The electronic energy spectrum of middle Mn ion.
Fig. 2. LiMn after functional polymer is modified under the normal temperature 2O 4The charging and discharging curve of/Li battery.Abscissa is a specific capacity, and mAh/g, ordinate are voltage, V.
Fig. 3. LiMn after functional polymer is modified under the normal temperature 2O 4The cycle life of/Li.Abscissa is the charge and discharge cycles number of times, and ordinate is a discharge capacity, mAh.Curve 1 is the LiMn of unmodified among the figure 2O 4The discharge capacity of/Li battery, curve 2 is the LiMn of functional polymer after modifying 2O 4The discharge capacity of/Li battery.
LiMn after modifying under Fig. 4 .55 ℃ high temperature 2O 4The cycle life of/Li.Abscissa is the charge and discharge cycles number of times, and ordinate is a discharge capacity, mAh.Curve 1 is the LiMn of unmodified among the figure 2O 4The discharge capacity of/Li battery, curve 2 is the LiMn of functional polymer after modifying 2O 4The discharge capacity of/Li battery.
Fig. 5 .55 ℃ LiMn 2O 4The cycle characteristics of/C battery.Abscissa is the charge and discharge cycles number of times, and ordinate is a discharge capacity, mAh.
Below further specify beneficial effect of the present invention by embodiment, but should not be construed as is limitation of the present invention, and the technical scheme that modification, replacement or change realized of every other various ways of being made based on technology basic thought of the present invention all belongs to scope of the present invention.
Embodiment
The LiMn that embodiment 1 functional polymerization is modified 2O 4The preparation of the employed polymer of electrode slice
With monomer acrylonitrile (AN): the ratio that the mass ratio of monomer N-vinyl pyrrolidones (NVP) is respectively 7: 2,5: 4,6: 3,8: 7 and 8: 5 adds reactor, press monomer gross mass 1%, 3%, 5%, 5% ratio adds initiator A IBN, add a certain amount of secondary deionized water, feed nitrogen half an hour, to remove the oxygen in the reaction system.Heating and constant temperature to 65 ℃ reacts and finish reaction after 6 hours, and prepared polymer is carried out suction filtration, and in vacuum drying chamber, dry obtain containing can with the polymer of the functional group of Mn ion complexation ability.
Embodiment 2
The preparation method of the polymer of present embodiment is with embodiment 1, its difference is to increase acrylamide (AM) monomer, the quality proportioning of its reaction raw materials is respectively AN: AM: NVP=5: 4: 2,6: 4: 1 and 7: 3: 1, prepared polymer was the white powder solid.
Embodiment 3
In oil phase, carry out the polymer that copolymerization obtains being used to modify the LiMn2O4 functional material with monomer acrylamide (AM) and monomer along 2-crotonic anhydride (MAH) in the present embodiment, the quality proportioning of its reaction raw materials is: AM: MAH=1.3: 1.0, and product is a white solid.
The method for making of above-mentioned functional material polymer for modifying the LiMn2O4 electrode is: add 10 parts along 2-crotonic anhydride and 30 parts of butanone at reaction vessel, and stirring and dissolving, 100 rev/mins of rotating speeds passed into nitrogen flooding oxygen 1 hour; Heating and constant temperature are in 60 ℃; Add then 5 parts of initator azodiisobutyronitriles; In constant pressure funnel, add 13 parts of acrylamides and 50 parts of butanone, time for adding 4 hours; React end in 8 hours.Make the polymer of above-mentioned composition.
Embodiment 4
The method for making and the operating condition of present embodiment polymer are substantially the same manner as Example 3, and only different is to increase a kind of monomer acrylonitrile (AN), is added in the constant pressure funnel.The quality proportioning of its reaction raw materials is: AM: MAH: AN=1.3: 1.0: 0.5, polymer was a white solid.
Embodiment 5
The method for making of present embodiment polymer is same as embodiment 3, and only not being both a kind of monomer of increase is styrene (ST), is added in the constant pressure funnel, 4 hours dropping time, reacts end in 6 hours.The quality proportioning of its reaction raw materials is: AM: MAH: ST=1.3: 1.0: 0.2, polymer was a white solid.
The LiMn that embodiment 6 functional polymers are modified 2O 4The preparation of electrode slice
A. take by weighing mass percent concentration and be 15% LA132 aqueous binder (Chengdu Yindile Power Source Science and Technology Co., Ltd's production) 100 grams, add deionized water 200 grams, LiMn 2O 4450 grams, conductive black 35 grams place homogenizer to stir and got finely dispersed slurry in 4～12 hours, are coated in slurry on the aluminium foil then and dry moisture to obtain LiMn 2O 4Electrode slice, wherein aluminum foil thickness is 20 μ m, LiMn 2O 4Coating layer thickness is 200 μ m, uses then roller with LiMn 2O 4Coating layer thickness is rolled to 130 μ m by 200 μ m, obtains LiMn 2O 4Pole piece.
B. making mass percent concentration with the polymer dissolution of embodiment 2 preparation in DMF (DMF) is 5% or 20% polymer solution, again this polymer solution is coated in LiMn 2O 4On the pole piece, namely get the LiMn that functional polymer is modified behind the volatilization DMF 2O 4Electrode slice.
To LiMn 2O 4Made XPS analysis before and after electrode slice is modified, Fig. 1 is the photoelectron spectroscopy figure of manganese ion before and after pole piece is modified.As can be seen from the figure, the LiMn of modified processing not 2O 4, its manganese ion two absworption peaks occurred at 641.300eV and 652.719eV place.And through the LiMn after the processing of functional polymer decorations 2O 4Pole piece, the absworption peak of its manganese ion lays respectively at 641.870eV and 653.277eV, with the LiMn of modified processing not 2O 4Compared respectively displacement 0.570eV and 0.558eV, obvious displacement has taken place in its electron binding energy, proves absolutely to exist certain valence link effect between manganese ion and the functional polymer, and namely the two can reach well complexing.
Embodiment 7 thermal polymerization methods prepare polymer-modified LiMn of the present invention 2O 4Electrode slice
Take by weighing mass percent concentration and be 15% LA132 aqueous binder 100 grams, add deionized water 200 grams, LiMn 2O 4450 grams, conductive black 35 grams, two propionitrile 6 grams of acrylamide, NVP 3 can, initiator A IBN 0.2 gram places homogenizer to stir and got finely dispersed slurry in 4～12 hours, then slurry is coated on the aluminium foil and at 60～80 ℃ and dries moisture, aluminum foil thickness is 20 μ m, LiMn 2O 4Coating layer thickness is 200 μ m, is using roller with LiMn 2O 4Coating layer thickness is rolled to 130 μ m by 200 μ m.Electrode slice after rolling was namely got polymer-modified LiMn in 4 hours in 90～120 ℃ of processing of temperature 2O 4Electrode slice.
Embodiment 8
The method for making of present embodiment is same as embodiment 7, only is not both with the two propionitrile of acrylamide diacetone instead of propylene acid amides.
Embodiment 9
The method for making of present embodiment is same as embodiment 7, and only different is to increase a kind of monomer methylene-bisacrylamide 2 grams.
The LiMn that modifies with the functional polymer of embodiment 7 preparation 2O 4Electrode is anodal, take lithium metal as negative pole or Delanium be negative pole, be assembled into test lithium battery and lithium ion battery take the Cellgard-2400 microporous barrier as battery diaphragm.The test result of test lithium battery and lithium ion battery is seen Fig. 2,3,4 and 5.
Fig. 2 is through modifying the LiMn after processing 2O 4Charging and discharging curve at normal temperatures, the LiMn after the modification 2O 4Its platform of first charge-discharge curve is not obvious at normal temperatures, and its charge/discharge capacity is also on the low side, and its reason mainly is the process that there is a swelling activation in polymer.Be the 3rd～8 time charging and discharging curve figure shown in the figure, on scheming, can find out, modify through functional polymer and process rear LiMn 2O 4On charging and discharging curve, still there are respectively two fairly obvious charge and discharge platform, respectively corresponding LiMn 2O 4Second order take off lithium and embedding lithium process.The macromolecule modified LiMn of this functions 2O 4Electrode does not affect LiMn 2O 4Chemical property.
Fig. 3 processes rear specific capacity change curve under normal temperature condition, as can be seen from the figure undressed LiMn through modifying 2O 4Decay to 94.8mAh/g through specific capacity after 50 circulations by 118.7mAh/g at normal temperatures, its specific capacity has lost 20.1%; And process rear LiMn through modifying 2O 4Capacity is on the low side first for it, and 117.2mAh/g is only arranged, and for the second time circulation reaches maximum, and its specific capacity is 120.9mAh/g.Its specific capacity drops to 109.8mAh/g by 120.9mAh/g, and its specific capacity has only lost 9.2%, and this illustrates after modified treatment, has strengthened LiMn 2O 4The stability of structure has improved Li +Deviate from and embed invertibity.
Fig. 4 modifies LiMn 2O 4Electrode and unmodified LiMn 2O 4The specific capacity of electrode under high temperature (55 ℃) condition changes comparative graph.The LiMn of unprocessed modification 2O 4Under hot conditions, shown relatively poor cycle performance.After 100 circulations, its specific capacity drops to 35.2mAh/g, has only kept 30.2% of specific capacity first.And through modifying the LiMn after processing 2O 4Its specific capacity still remains on 69.1mAh/g, and capacity has only descended 42.5%, has shown preferably cyclical stability.
Fig. 5 adopts functional polymer to modify LiMn 2O 4The charge and discharge cycles figure of the lithium ion battery of electrode assembling under 55 ℃ of conditions.Use the LiMn of this modification 2O 4The lithium ion battery of electrode assembling has presented good high temperature charge and discharge cycles stability.This explanation adopts functional polymer to modify LiMn 2O 4LiMn in the time of can overcoming high temperature 2O 4The problem of capacity attenuation can solve restriction LiMn 2O 4Application obstacle in the commodity lithium ion battery.The enforcement of this technology path will produce bigger influence to solving anode material for lithium-ion batteries source, price, environmental protection, fail safe etc.
In a word, functional polymer provided by the invention is modified LiMn 2O 4Electrode has overcome LiMn 2O 4After inorganic oxide and conducting polymer coating, the problem and the separating twice problem that cause gram volume to descend; And utilize polymer can with the complexing of Mn ion, reduce the oxidative decomposition of electrolyte, reduce the stripping of manganese ion, thereby improve the battery high-temperature cyclical stability; Implementing process is simple, has preferably industrialization value.

Claims (8)

1, a kind of anode material for lithium-ion batteries is characterized in that: it is the LiMn that is modified by functional polymer 2O 4Electrode slice; Described functional polymer contain can with the functional group of Mn ion complexation, be by one or more contain-CN ,-CON-,-CO-or-polymerization of vinyl monomer of COO-group forms.
2, anode material for lithium-ion batteries according to claim 1 is characterized in that:
The vinyl monomer of described containing-CN group is: acrylonitrile, methacrylonitrile or inclined to one side dicyano ethene; Contain-vinyl monomer of CON-group is: acrylamide, acrylamide diacetone, the two propionitrile of acrylamide, acrylamide list propionitrile or methylene-bisacrylamide; Contain-vinyl monomer of CO-group is: N-vinyl pyrrolidone or general formula are CH 2=CH (CH 2) ketone of nCOR, n=0 wherein, 1,2,3......, R are all kinds of alkyl; Contain-vinyl monomer of COO-group is: anhydrides vinyl monomer or general formula are CH 2=CH (CH 2) the ester class vinyl monomer of nCOOR, n=0 wherein, 1,2,3......, R are all kinds of alkyl.
3, prepare the method for the described anode material for lithium-ion batteries of claim 1, it is characterized in that: use the solution impregnation of functional polymer or apply LiMn 2O 4Electrode, solvent flashing obtains the LiMn that functional polymer is modified 2O 4
4, the preparation method of anode material for lithium-ion batteries according to claim 3, it is characterized in that: the solution of described functional polymer is prepared from by following method: 5～40 parts of weight are contained-CN,-CON-,-CO-or-vinyl monomer of COO-group two or more add in reactors, the solvent that adds 50～300 parts of weight again, stir, in adding monomer gross mass 1%～5% ratio adding initator, feeding nitrogen is removed the oxygen in the reaction system, heating and constant temperature to 45～80 ℃, react and finish reaction after 2～48 hours, with prepared polymer suction filtration, drying obtain containing can with the polymer of the functional group of Mn ion complexation ability, again polymer dissolution is obtained the solution of functional polymer in polar organic solvent.
5, the preparation method of anode material for lithium-ion batteries according to claim 4 is characterized in that: the mass percent concentration of the solution of described functional polymer is 5-20%.
6, prepare the method for the described anode material for lithium-ion batteries of claim 1, it is characterized in that: at preparation LiMn 2O 4Add during electrode contain-CN ,-CON-,-CO-or-vinyl monomer and the initator of COO-group, make the LiMn that contains polymerisable monomer 2O 4Electrode slice carries out this electrode slice thermal polymerization again or uses the UV-irradiation initiated polymerization to obtain the LiMn that functional polymer is modified under 60～150 ℃ temperature 2O 4Electrode slice.
7, the method for preparing anode material for lithium-ion batteries according to claim 6 is characterized in that: the LiMn that contains polymerisable monomer 2O 4Electrode slice be with contain-CN ,-CON-,-CO-or-vinyl monomer and the initator of COO-group join LiMn 2O 4, be mixed together in the slurry that forms of conductive agent and adhesive to be coated on the aluminium foil after stirring and obtain.
8, a kind of lithium ion battery is characterized in that: done anodally by the described anode material for lithium-ion batteries of claim 1, take Delanium or native graphite as negative pole, polymer microporous film is battery isolating film, LiPF 6Organic solution consist of lithium ion battery as electrolyte.
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CA2534243A1 (en) * 2006-01-25 2007-07-25 Hydro Quebec Coated metal oxide particles with low dissolution rate, methods for their preparation and use in electrochemical systems
CN102569723A (en) * 2012-02-13 2012-07-11 华为技术有限公司 Lithium ion battery positive electrode material and preparation method thereof, positive electrode and lithium ion battery
CN103682355A (en) * 2012-09-18 2014-03-26 华为技术有限公司 Compound silicate anode material and lithium battery and preparation methods thereof, and communication equipment
CN103022484B (en) * 2012-12-15 2014-08-27 华中科技大学 Lithium iron conductive complex modified lithium iron phosphate anode material and preparation method thereof
CN106558698B (en) * 2015-09-29 2020-03-20 比亚迪股份有限公司 Lithium ion battery positive electrode slurry, lithium ion battery positive electrode plate, preparation methods of lithium ion battery positive electrode slurry and positive electrode plate, and lithium ion battery
CN105633412A (en) * 2016-04-05 2016-06-01 宁德新能源科技有限公司 Positive material and lithium ion battery adopting same
CN108767322B (en) * 2018-05-22 2021-01-15 浙江锋锂新能源科技有限公司 Preparation method of all-solid-state battery core
CN110336018B (en) * 2019-07-16 2022-05-31 合肥融捷能源材料有限公司 Modified nickel cobalt lithium manganate material and preparation method and application thereof
CN113471401B (en) * 2021-05-28 2023-07-18 上海空间电源研究所 High-safety high-load lithium ion electrode plate and manufacturing method thereof
CN114264967A (en) * 2021-12-14 2022-04-01 哈尔滨工业大学 Method and system for rapidly estimating retired battery residual energy based on capacity loss mechanism

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