CN102420323A - Electrode composite material of lithium secondary battery and preparation method thereof - Google Patents

Electrode composite material of lithium secondary battery and preparation method thereof Download PDF

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CN102420323A
CN102420323A CN2011100512330A CN201110051233A CN102420323A CN 102420323 A CN102420323 A CN 102420323A CN 2011100512330 A CN2011100512330 A CN 2011100512330A CN 201110051233 A CN201110051233 A CN 201110051233A CN 102420323 A CN102420323 A CN 102420323A
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lithium
secondary battery
graphene
lithium secondary
composite material
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CN102420323B (en
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刘兆平
唐长林
周旭峰
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses an electrode composite material of a lithium secondary battery and a preparation method thereof. The electrode composite material comprises lithium secondary battery electrode active materials, graphene and conductive materials. Because graphene has good electronic conductivity, the electronic conductivity of the electrode composite material is increased. In addition, the electrode composite material provided by the invention comprises conductive materials having high conductivity, thus the conductivity of the electrode composite material is further increased. The electrode composite material of the lithium secondary battery is prepared by using the combination of lithium secondary battery electrode active materials, graphene and conductive materials, has good conductivity. The experiment results prove that the electronic conductivity of the electrode composite material can reach 0.87 S/cm, and the ion diffusion coefficient can reach 8.4*10<-8> cm<2>/S.

Description

Electrode composite material of lithium secondary battery and preparation method thereof
Technical field
The present invention relates to the energy storage material technical field, more particularly, relate to electrode composite material of a kind of lithium secondary battery and preparation method thereof.
Background technology
In recent years, along with highlighting of the problems such as exhausted day by day and global warming of resource, the life style of green low-carbon has received to be advocated.Wherein, to come part to replace the internal-combustion engines vehicle of consumption of fossil fuels be one of main method that solves energy crisis and ecological deterioration to development electric motor car and hybrid electric vehicle.Driving power is to influence the critical component that electric motor car is promoted the use of, and nowadays widely used driving power comprises lead-acid battery, ni-mh/NI-G, lithium secondary battery etc.Advantages such as in various driving powers, lithium secondary battery is owing to have the energy density height, and cyclicity is good, and self-discharge rate is low, long service life and environmental pressure are little have obtained extensive studies.
The electrode material of lithium secondary battery comprises positive electrode and negative material.The negative material of lithium secondary battery comprises graphite, metal simple-substance, alloy, semimetal, metal oxide, metal nitride and metal sulfide etc.Graphite is modal negative material in the present lithium secondary battery; Metal and alloy thereof, for example Li metal and alloy thereof, Ni sill and Zn sill etc. are the negative materials that is used the earliest in the lithium secondary battery; Semi-metallic is enhanced than the specific capacity of graphite, and the specific energy that improves secondary cell is had the important strategic meaning; Metal oxide, metal nitride, metal sulfide can be expressed as M mX n, wherein X is O, S; Or N, M is selected from Li, Na; Among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P one or more; 0＜m＜10,0＜n＜10, and select combination between the M, X, m, n to guarantee M mX nBe electric neutrality.But the conductivity of above-mentioned negative material is unsatisfactory.
The positive electrode of lithium secondary battery comprises metal oxide and the polyanion material that contains lithium.The lithium metal oxide that contains commonly used comprises cobalt acid lithium, LiMn2O4, rich lithium stratiform nickel LiMn2O4 and lithium nickelate etc., and wherein the conductivity of cobalt acid lithium is 10 -2The conductivity of S/cm, rich lithium stratiform nickel LiMn2O4 is 10 -4The conductivity of S/cm, lithium nickelate is 10 -3S/cm.But, contain lithium metal oxide when high current charge-discharge, have safety problem easily, need to adopt this moment some to have high electrical conductivity but the material of electrochemistry inertia carry out compound, thereby improve serviceability.
The general formula of polyanion material is A aM ' B 'M b(X cY d) eZ f, wherein, A is Li, and 0＜a＜8; M is one or more metals, and at least a metal wherein can be oxidizing to higher valence state, comprises at least a in iron, aluminium, titanium, cobalt, boron, chromium, nickel, magnesium, zirconium, gallium, vanadium, manganese and the zinc and 0＜b≤5; M ' can occupy the position of A or M or occupy both positions simultaneously; Comprise 1～4 valence metal ion; As, one or more among alkali metal ion, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn and the Pb, 0≤b '≤5; At X cY dIn, X is selected from one or more among P, As, Sb, Si, Ge, V, the S, and Y is selected from one or more among S, O, the N, 0＜c≤5,0＜d≤10; Z is an option, comprises OH, one or more among halogen, N, the S, 0＜f≤10; Wherein, to A, M, M ', X, Y, Z, a, b, b ', c, d, e, f select to keep compound to be electric neutrality.Owing to contain polyanion in the polyanion material, therefore have very strong structural stability, security performance is higher, is suitable for the electrode material as electrokinetic cell.But then; Strong chemical bonding effect between polyanion and transition metal ions and the lithium metal ion; Cause the electric conductivity of this material relatively poor; Be difficult to carry out high current charge-discharge, therefore need be through variety of way as adding the high rate performance that electronic conductive material and/or ion conductive material improve this material.
At publication number is in the Chinese patent document of CN101453020A, and the M A Ermeng of Quebec, CAN water power company proposes to use RESEARCH OF PYROCARBON to coat the polyanion material, makes conductivity of electrolyte materials reach 10 -8S/cm; In patent CN1652999A, people such as Jeremy's Bark of Willens Technologies, Inc. propose to use carbon thermal reduction to prepare the polyanion material, have improved the conductivity of polyanion material to a certain extent; But; It is unsatisfactory that this polyanion material gets electric conductivity, during former because preparation polyanion material, will undergo phase transition for fear of the polyanion material; Employed heat treatment temperature is generally 600～750 ℃; But,, determine the Sp of the electric conductivity of RESEARCH OF PYROCARBON material when heat treatment temperature is 750 degree when following 2The degree of graphitization of hydridization is lower usually.In patent CN101345099A, the Liao Benjie of Advanced Lithium Electrochemis proposes the electric conductivity of the eutectic raising polyanion material of use oxide, and still, the electric conductivity of single oxide material is still lower.
Grapheme material is one type and has individual layer or which floor sp of minority 2The lonsdaleite material of hydridization, interlayer combines with π key form in the sandwich construction, because this electron-like is a diracelectron near Fermi's ability, effective mass is zero, so conductivity reaches 10 6S/cm is the human at present the highest material of finding of electric conductivity.Application number be 200910155316.7 with application number be in 201010226062.6 the Chinese patent document; The Liu Zhao equality proposition use Graphene and the polyanion material of Ningbo Material Technology and Engineering Inst. of the Chinese Academy of Sciences are compound, have improved the electric conductivity of this composite material.
The inventor considers, a kind of electrode composite material of lithium secondary battery is provided, and this composite material is compared with negative material with above-mentioned positive electrode material of lithium secondary cell, can further improve the electric conductivity of lithium secondary battery material.
Summary of the invention
In view of this, the electrode composite material that the present invention provides the technical problem that will solve to be to provide a kind of lithium secondary battery, this composite material has higher electric conductivity.
The present invention provides a kind of electrode composite material of lithium secondary battery, comprising:
Lithium secondary battery electrode active material, Graphene and electric conducting material,
Said electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation mX n, conjugated structure conducting polymer and conductivity greater than 10 -10In the ionic conduction type material of S/cm one or more,
Wherein, X is O, S or N; M is Li, Na, one or more among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P; 0＜m＜10,0＜n＜10.
Preferably, said ionic conduction type material is:
Contain lithium VI main group compound, contain VII main group compound, the LiTi of lithium 2(PO 4) 3, LiGe 2(PO 4) 3, Li pM rX q, contain the VI main group compound of lithium derivative, contain derivative, the LiTi of the VII main group compound of lithium 2(PO 4) 3Derivative, LiGe 2(PO 4) 3Derivative and Li pM rX qDerivative in one or more, M is one or more among P, C, the S, X is O and/or S, p, q and r are positive number.
Preferably, the conducting polymer of said conjugated structure is polyaniline, polyacetylene, polypyrrole, polythiophene or polyphenylene sulfide.
Preferably, the mass ratio of said lithium secondary battery electrode active material, Graphene and electric conducting material is 80～99: 0.01～10: 0.01～10.
Preferably; Said lithium secondary battery electrode active material is positive electrode active materials and/or negative active core-shell material; Said positive electrode active materials comprises polyanion material and the metal oxide that contains lithium, and said negative active core-shell material is that intermediate value discharges and recharges the active material of the potential difference of the relative lithium metal of current potential less than 2V.
Preferably, said negative active core-shell material is a kind of in graphite, metal simple-substance, alloy, semimetal, metal oxide, metal nitride and the metal sulfide and several kinds.
Preferably, said polyanion material is a LiFePO4, and said metal oxide is a manganese Base Metal oxide, and said negative material is silicon, tin, Si oxide and/or tin-oxide.
Preferably, said Graphene is that individual layer or the number of plies are that carbon atom is with sp between 1 to 20 layer, in the layer 2Hybridized orbit is formed hexagon honeycomb lattice, interlayer is the laminar material with carbon element that carbon atom combines with the π key; One or more grapheme material and/or intercalated graphite alkene in fluorine-containing, nitrogen, oxygen, carbonyl, carboxyl and the hydroxyl.
Preferably, said lithium secondary battery electrode active material, Graphene and electric conducting material coexist with the form of mixing, compound, eutectic and/or physics contacts.
The present invention also provides a kind of preparation method of electrode composite material of lithium secondary battery, comprising:
Lithium secondary battery electrode active material or its presoma, Graphene, electric conducting material or its presoma are mixed, and heat treatment under 200～900 ℃, non-oxidizing atmosphere then obtains the electrode composite material of lithium secondary battery,
Said electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation mX n, conjugated structure conducting polymer and conductivity greater than 10 -10In the ionic conduction type material of S/cm one or more,
Wherein, X is O, S or N; M is Li, Na, one or more among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P; 0＜m＜10,0＜n＜10.
Preferably, said ionic conduction type material is:
Contain lithium VI main group compound, contain VII main group compound, the LiTi of lithium 2(PO 4) 3, LiGe 2(PO 4) 3, Li pM rX q, contain the VI main group compound of lithium derivative, contain derivative, the LiTi of the VII main group compound of lithium 2(PO 4) 3Derivative, LiGe 2(PO 4) 3Derivative and Li pM rX qDerivative in one or more, M is one or more among P, C, the S, X is O and/or S, p, q and r are positive number.
Preferably, the mass ratio of said lithium secondary battery electrode active material, Graphene and electric conducting material is 80～99: 0.01～10: 0.01: 10.
Preferably; Said lithium secondary battery electrode active material comprises positive electrode active materials and/or negative active core-shell material; Said positive electrode active materials comprises polyanion material and the metal oxide that contains lithium, and said negative material is that intermediate value discharges and recharges the active material of the potential difference of the relative lithium metal of current potential less than 2V.
Preferably, said Graphene is that individual layer or the number of plies are that carbon atom is with sp between 1 to 20 layer, in the layer 2Hybridized orbit is formed hexagon honeycomb lattice, and interlayer is the laminar material with carbon element that carbon atom combines with the π key; One or more grapheme material and/or intercalated graphite alkene in fluorine-containing, nitrogen, oxygen, carbonyl, carboxyl and the hydroxyl.
Preferably, said heat treatment time is 0.2～50 hour.
Can find out that from above-mentioned technical scheme the present invention provides electrode composite material of a kind of lithium secondary battery and preparation method thereof, said electrode composite material comprises: lithium secondary battery electrode active material, Graphene and electric conducting material.Graphene and electric conducting material are distributed between surface of active material and active material particle, have formed the electrode composite material of said lithium secondary battery.Because Graphene has electron conduction preferably, therefore, has improved the electron conduction of electrode composite material.In addition, also comprise electric conducting material in the electrode composite material provided by the invention, thereby further improved the conductivity of electrode composite material with higher conductivity.Therefore, the electrode composite material of lithium secondary battery provided by the invention adopts lithium secondary battery electrode active material, the Graphene form mutually compound with electric conducting material, has good electrical conductivity.Experimental result proves that the electronic conductivity of electrode composite material provided by the invention can be up to 0.87S/cm, and ionic diffusion coefficient can be up to 8.4 * 10 -8Cm 2/ S.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is LiFePO 4, the embodiment of the invention 2 preparation LiFePO 4/ Graphene/C and LiFe 0.99Mg 0.01PO 4/ Graphene/C/Li 3PO 4XRD figure;
Fig. 2 is the LiFePO of the embodiment of the invention 2 preparations 4The SEM photo of/Graphene/C;
Fig. 3 is the LiFePO of the embodiment of the invention 2 preparations 4The SEM photo of/Graphene/C;
Fig. 4 is the LiFe of embodiment of the invention preparation 0.99Mg 0.01PO 4/ Graphene/C/Li 3PO 4The TEM photo;
Fig. 5 is LiFePO 4LiFePO with the embodiment of the invention 2 preparations 4The I-V performance plot of/Graphene/C;
Fig. 6 is LiFePO 4, LiFePO 4The LiFePO of/Graphene, the embodiment of the invention 2 preparations 4The LiFe of/Graphene/C and embodiment of the invention preparation 0.99Mg 0.01PO 4/ Graphene/C/Li 3PO 4The charge-discharge performance curve;
Fig. 7 is LiMn 2O 4And LiMn 2O 4The XRD figure of/Graphene;
Fig. 8 is LiMn 2O 4LiAl with embodiment of the invention preparation 0.02Mn 1.98O 4/ Graphene/Li 3PO 4The SEM photo;
Fig. 9 is LiMn 2O 4LiAl with embodiment of the invention preparation 0.02Mn 1.98O 4/ Graphene/Li 3PO 4The SEM photo;
Figure 10 is LiMn 2O 4LiAl with embodiment of the invention preparation 0.02Mn 1.98O 4/ Graphene/Li 3PO 4Charging and discharging curve;
Figure 11 is the SEM photo of the Si/ Graphene/C of the embodiment of the invention 20 preparations;
Figure 12 is the SEM photo of the Si/ Graphene/C of the embodiment of the invention 20 preparations;
Figure 13 is the SEM photo of the Si/ Graphene/C of the embodiment of the invention 20 preparations;
Figure 14 is the SEM photo of the Si/ Graphene/C of the embodiment of the invention 20 preparations;
Figure 15 is the charging and discharging curve of the Si/ Graphene/C of Si/C and the embodiment of the invention 20 preparations.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The embodiment of the invention discloses a kind of electrode composite material of lithium secondary battery, comprising:
Lithium secondary battery electrode active material, Graphene and electric conducting material,
Said electric conducting material is that nitride, organic conductive material and the conductivity of nitride, Au of nitride, the Pt of nitride, the Cu of sulfide, the Ag of sulfide, the Au of sulfide, the Pt of sulfide, the Cu of oxide, the Ag of oxide, the Au of oxide, the Pt of oxide, the Cu of graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive black, conductive carbon material, Ag, Cu, Pt, Au, Ag is greater than 10 -8In the ionic conduction type material of S/cm one or more.
Said lithium secondary battery electrode active material preferably includes positive electrode active materials and/or negative active core-shell material; Said positive electrode active materials comprises polyanion material and the metal oxide that contains lithium, and said negative active core-shell material is preferably intermediate value and discharges and recharges the active material of the potential difference of the relative lithium metal of current potential less than 2V.
Among the present invention, said polyanion material is an electrochemical active material, and general formula is A aM ' B 'M b(X cY d) eZ f, wherein, A is Li, and 0＜a＜8; M is preferably one or more metals, and at least a metal wherein can be oxidizing to higher valence state, comprises at least a in iron, aluminium, titanium, cobalt, boron, chromium, nickel, magnesium, zirconium, gallium, vanadium, manganese and the zinc, 0＜b≤5; M ' can occupy the position of A or M or occupy both positions simultaneously; Preferably include 1～4 valence metal ion; As, one or more among alkali metal ion, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, the Pb, 0≤b '≤5; X cY dIn, wherein X is selected from one or more among P, As, Sb, Si, Ge, V, the S, and Y is selected from one or more among S, O, the N, 0＜c≤5,0＜d≤10; Z is an option, comprises OH, one or more among halogen, N, the S, 0＜f≤10; Wherein, to A, M, M ', X, Y, Z, a, b, b ', c, d, e, f select to keep compound to be electric neutrality.
It is A that the above-mentioned metal oxide that contains lithium has general formula aM bM ' cO dZ f,
A wherein, b, c, d is non-vanishing, is the numerical value between 1～10, and A preferably includes Li, Na, one or more in the alkali metal such as K, Mg, Ca, Al; M preferably includes transition metal, more preferably one or more in manganese, iron, cobalt, nickel, vanadium, molybdenum, titanium, the zirconium; M ' can occupy the position of A or M or occupy both positions simultaneously; Be preferably 1～4 valence metal ion; One or more of alkali metal ion, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Pb etc. more preferably, 0≤b '≤5; Z is preferably OH, one or more among halogen, N, the S, and the metal oxide of said lithium is electric neutrality.
The metal oxide of lithium described in the present invention is the molybdenum oxide of lithiumation more preferably, the barium oxide of lithiumation, the Mn oxide of lithiumation, the cobalt/cobalt oxide of lithiumation, the titanium oxide of lithiumation, the nickel oxide of lithiumation and be doped the derivative with modification.
Above-mentioned negative active core-shell material is preferably intermediate value and discharges and recharges the active material of the potential difference of the relative lithium metal of current potential less than 2V; Be preferably a kind of in graphite, metal simple-substance, alloy, semimetal, metal oxide, metal nitride and the metal sulfide and several kinds, specifically comprise lithium metal, material with carbon element, can form material, metal oxide, metal sulfide of alloy etc. with lithium.Described material with carbon element can be organic high molecular compound of graphite, RESEARCH OF PYROCARBON, coke, active carbon, carbon fiber and high temperature sintering etc.Describedly can be metallic element with the material that lithium forms alloy, for example Mg, B, Al, Ga, In, Si, Sn, Pb, Sb, Bi, Cd, Ag, Zn, Hf, Zr, Y etc. contain the alloy of Si and Sn, for example SiB 4, SiB 6, Mg 2Si, Mg 2Sn, Ni 2Si, TiSi 2, MoSi 2, CoSi 2, NiSi 2, CaSi 2, CrSi 2, Cu 5Si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2And ZnSi 2Deng; And other active materials, like SiC, Si 3N 4, Si 2N 2O, Ge 2N 2O, SiO x(0＜x≤2), SnO x(0＜x≤2), LiSiO and LiSnO etc.Said metal oxide, metal sulfide can be expressed as M mX n(X=O, S, or N) comprises being expressed as M mX n(X=O, S, or N); Wherein M is selected from Li; Na, one or more among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P, 0＜m＜10; 0＜n＜10, and select combination between the M, X, m, n to guarantee M mX nBe electric neutrality, especially comprise SnO, SnO 2, SiO 2The compound of sill, oxide and metal is like Si/SiO 2Compound, Sn/SnO, Sn/SnO 2
Graphene is one type and has individual layer or which floor sp of minority 2The lonsdaleite material of hydridization, interlayer combines with π key form in the sandwich construction, because this electron-like is a diracelectron near Fermi's ability, effective mass is zero, so conductivity reaches 10 6S/cm is the human at present the highest material of finding of electric conductivity.Described Graphene is that the individual layer or the number of plies are between 1 to 20 layer, is that carbon atom is with Sp in the layer 2Hybridized orbit is formed hexagon honeycomb lattice, the laminar material with carbon element that interlayer combines with the π key.In addition, that the present invention has also comprised is fluorine-containing, one or more grapheme material and intercalated graphite alkene etc. in the nitrogen, oxygen, carbonyl, carboxyl, hydroxyl, and the grapheme material that comprises inevitable defective.
Electric conducting material described in the present invention is preferably electron conductive type or the ionic conduction type material except that Graphene, and the equal material preferably of electron conduction and ionic conductivity.Said electronic conductive material is specially conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation mX n, conjugated structure conducting polymer and conductivity greater than 10 -10In the ionic conduction type material of S/cm one or more, wherein, X is O; S or N, M are Li, Na; Among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P one or more; 0＜m＜10,0＜n＜10, and select combination between the M, X, m, n to guarantee M mX nBe electric neutrality.Said semimetal is preferably Si or Ge, and the conducting polymer of said conjugated structure is preferably one or more in polyaniline, polyacetylene, polypyrrole, polythiophene and the polyphenylene sulfide.
Said ionic conduction type material is the VI main group compound that contains lithium, VII main group compound, the LiTi that contains lithium 2(PO 4) 3, LiGe 2(PO 4) 3, Li pM rX q, contain the VI main group compound of lithium derivative, contain derivative, the LiTi of the VII main group compound of lithium 2(PO 4) 3Derivative, LiGe 2(PO 4) 3Derivative and Li pM rX qDerivative in one or more, M is one or more among P, C, the S, X is O and/or S, p, q and r are positive number.
The mass ratio of said lithium secondary battery electrode active material, Graphene and electric conducting material is preferably 80～99: 0.01～10: 0.01～10, more preferably 85～99: 0.1～5: 0.1～10, most preferably be 90～99: 1～3: 1～5.
Graphene described in the present invention and electric conducting material are distributed between surface of active material and active material particle through one or more way of contact coexistence forms that even mixing, compound, parcel, eutectic, physics contact.Because Graphene has electron conduction preferably, therefore, has improved the electron conduction of electrode composite material.In addition, also comprise electric conducting material in the electrode composite material provided by the invention, thereby further improved the conductivity of electrode composite material with higher conductivity.
The present invention also provides a kind of preparation method of electrode composite material of lithium secondary battery, comprising:
Lithium secondary battery electrode active material or its presoma, Graphene, electric conducting material or its presoma are mixed, and heat treatment under 200～900 ℃, non-oxidizing atmosphere then obtains the electrode composite material of lithium secondary battery,
Said electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation mX n, conjugated structure conducting polymer and conductivity greater than 10 -10In the ionic conduction type material of S/cm one or more,
Wherein, X is O, S or N; M is Li, Na, one or more among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P; 0＜m＜10,0＜n＜10.
Lithium secondary battery electrode active material precursor compound according to the invention and electric conducting material precursor compound are precursor compound as known in the art.
Said lithium secondary battery electrode active material comprises positive electrode active materials and/or negative active core-shell material; Said positive electrode active materials comprises polyanion material and the metal oxide that contains lithium, and said negative material is that intermediate value discharges and recharges the active material of the potential difference of the relative lithium metal of current potential less than 2V.
Said ionic conduction type material is the VI main group compound that contains lithium, VII main group compound, the LiTi that contains lithium 2(PO 4) 3, LiGe 2(PO 4) 3, Li pM rX q, contain the VI main group compound of lithium derivative, contain derivative, the LiTi of the VII main group compound of lithium 2(PO 4) 3Derivative, LiGe 2(PO 4) 3Derivative and Li pM rX qDerivative in one or more, M is one or more among P, C, the S, X is O and/or S, p, q and r are positive number.
The mass ratio of said lithium secondary battery electrode active material, Graphene and electric conducting material is preferably 80～99: 0.01～10: 0.01～10, more preferably 85～99: 0.1～5: 0.1～10, most preferably be 90～99: 1～3: 1～5.
Said non-oxygen atmosphere is preferably one or more in argon gas, nitrogen, hydrogen, carbon monoxide and the carbon dioxide.Said heat treatment temperature is preferably 300～800 ℃, more preferably 400～700 ℃.Said heat treatment time is preferably 0.2～50 hour, and more preferably 5～40 hours, more preferably 10～30 hours.
Hybrid mode of the present invention comprises that simple physics mixes, for example ball milling, grinding, ultra-fine mill, mix etc., said hybrid mode also preferably includes molecular level mixes, for example mix etc. the dissolving back.
The preparation method of the electrode composite material of lithium secondary battery provided by the invention can control the shape of the electrode composite material of the battery for preparing, and for example preferably adopts spray drying, deposition, co-precipitation, reunion and/or process for granulating preparation.When adopting spray drying, the electrode composite material of the lithium secondary battery for preparing be shaped as spherical agglomerates, it is of a size of 0.5～50 micron, each aggregate is made up of littler particle.
In the process of the electrode composite material for preparing said lithium secondary battery, preferably in the reactor that promotes the pressed powder balance, carry out; For example be selected from following reactor: the composition that the converter that fluid bed, converter, pusher furnace, belt drive, said reactor can control gaseous atmosphere and flowing.
Electric conducting material of the present invention is a material with carbon element, especially at the more equally distributed material with carbon element of particle surface, and the material with carbon element that preferably adopts organic matter pyrolysis to produce in the surface of active material original position.Wherein the RESEARCH OF PYROCARBON material of original position generation can improve the conductivity on active material particle surface; Graphene is used to improve the conductivity between the particle simultaneously; Therefore adopt Graphene and two kinds of electric conducting materials of RESEARCH OF PYROCARBON material, its conduction effect can be superior to wherein any one electric conducting material.
In another embodiment, electric conducting material of the present invention is that conductivity is greater than 10 -10The ionic conduction type material of S/cm.Because the ionic conduction type material has the effect of the ionic conductivity that improves the active material interface; Simultaneously Graphene is used to improve the conductivity between the particle, and the conductivity of the electrode composite material of the lithium secondary battery that is therefore formed by lithium secondary battery electrode active material, Graphene and ionic conduction type material is good.
The active material of lithium secondary battery electrode described in the present invention, electric conducting material are purchased from market, also can adopt the mode of preparation voluntarily.The preparation of electrode active material, electric conducting material can adopt method well known to those skilled in the art to prepare.
The preparation method of the polyanionic compound in the lithium secondary battery electrode active material according to the invention preferably adopts following method:
(1) chooses and contain transition metal ions compound, lithium salts and the polyanionic salt raw material that appraises at the current rate, take by weighing by stoichiometric proportion and be placed in the acetone dispersant, make solid content reach 10%-70%;
(2) in high energy ball mill, mix 1～20 hour after evenly, drying;
(3) mixture in (2) is placed atmosphere sintering furnace, be cooled to room temperature at 200～800 ℃ after handling 1h～48 hour down down, obtain required polyanion material in the non-oxidizing atmosphere protection;
(4) test this material electrochemical performance and conductivity.
Said lithium salts preferably includes lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium bromide, lithium fluoride, lithium nitride, contain one or more combination of the lithium salts of polyanion.The transition metal ions compound comprises transition metal oxide, sulfate, phosphate, nitrate, oxalates, acetate, citrate, contain one or more the combination in the slaine of polyanion.The combination of one or more of the slaine that polyanionic salt preferably includes the acid, ammonium salt, ester class, the hydro carbons that contain polyanion, contain polyanion.Wherein lithium, contain the metal ions M of appraising at the current rate, the mol ratio of polyanion is the content of being demarcated in the chemical formula, domain of walker for the metering ratio 80% to 120%;
The dispersant that the present invention adopts can also be one or more of water, alcohols, ketone, ethers, acids, Polymer Solution etc., and solvent quality is 0.3～10 times of other reactant presoma sums, and solid content is 5～60%, preferred 20%～40%.Spray drying adopts the means of direct drying or vacuum filtration to carry out.Above-mentioned heat treatment time can be preferably 1～48 hour heating time between 200～1000 ℃, preferred temperature is 600～800 ℃, and be 3～15 hours preferred heating time.
Metal oxide in the lithium secondary battery electrode active material according to the invention is with LiMn 2O 4For the preparation method of example following:
(1) choosing manganese dioxide, lithium carbonate raw material, Mn in molar ratio: Li is that 2: 1.05 ratio takes by weighing;
(2) mixture that step (1) is obtained mixes 7 hours after evenly in high energy ball mill, add dispersant in the process of lapping, drying;
(3) product that step (2) is obtained is cooled to room temperature behind 850 ℃ of heat treatment 5h, obtain required lithium manganate material, and the gained material is pure phase LiMn 2O 4
Electro-chemical test shows that when discharging and recharging under the 20mA/g current density, the capacity of this material is 110mAh/g, and conductivity of electrolyte materials is 5.1X10 -4S/cm.
When lithium secondary battery electrode active material according to the invention is negative active core-shell material, be example with silica/Graphene/material with carbon element, the preparation method is preferably:
Step (1) is with the compound of silicon; The compound of carbon containing and Graphene fully mix in ball mill; Add 30wt% grinding aid acetone simultaneously; Wherein Graphene is 1%～5% of a composition quality, and silica is 50%～90% of a composition quality, material with carbon element quality and be 3%～50% of composition quality;
Under nitrogen atmosphere protection, 200 ℃～1000 ℃ heat treatment is 1～20 hour in vacuum furnace, thereby obtains end-product silica/Graphene/material with carbon element composition with step (1) gained mixture for step (2).
Said material with carbon element can improve the nanometer degree of the electrode composite material of lithium secondary battery, suppresses the change in volume in the electrochemical process, and improves conductivity.Graphene can further improve the silica electron conduction, and has the better effect of " inhibition change in volume " of more common material with carbon element.Use Graphene and RESEARCH OF PYROCARBON material comprehensive silicon negative material, can improve the conductivity of negative active core-shell material, suppress the change in volume in the charge and discharge process, thereby reach the raising specific capacity, improve the effect of cycle life.The cost of the electrode composite material of the lithium secondary battery that therefore, prepares reduces.
Electrode composite material with lithium secondary battery provided by the invention is an electrode, prepares lithium secondary battery, and this battery will comprise positive pole, negative pole, electrolyte and barrier film, and one of them plants the electrode composite material that electrode is selected from lithium secondary battery provided by the invention.
Said barrier film is preferably the macromolecule membrane of porous, like microporous polypropylene film etc.Described nonaqueous electrolytic solution is made up of nonaqueous solvents and electrolyte.Said nonaqueous solvents (aprotogenic solvent) is preferably dimethyl carbonate, dipropyl carbonate, propene carbonate, ethylene carbonate, butylene, gamma butyrolactone, sulfolane, methyl sulfolane, 1; 2-dimethoxy-ethane, 1, the mixture of one or more in 2-diethoxyethane, oxolane, 2-methyltetrahydrofuran, methylpropanoic acid, methylbutanoic acid, acetonitrile, propionitrile, methyl phenyl ethers anisole, acetate, lactate and the propionic ester etc.Electrolyte is preferably the salt that contains lithium, like LiCl, LiBr, LiPF 6, LiClO 4, LiAsF 6, LiBF 4, LiCH 3SO 3, LiCF 3SO 3, LiN (CF 3SO 2) 2And LiB (C 6H 5) 4Deng.
The present invention preferably adopts following mode to test the chemical property and the conductivity of electrode composite material of the lithium secondary battery of the present invention preparation.
The test chemical property
With electrode composite material, Kynoar (PVDF), the conductive acetylene of the lithium secondary battery of the present invention preparation black be to join in N-methyl pyrrolidone at 80: 5: 15 by mass ratio; Magnetic agitation evenly after, positive plate is processed in oven dry, and with glove box in be assembled into 2032 button cells; Wherein negative pole is the lithium sheet; Barrier film is a polypropylene, and electrolyte is 1M LiPF6, and electrolyte quality is than being EC: DMC: EMC=1: 1: 1.
Probe temperature is 25 ℃, and voltage range is 2.0～4.2V, and the equipment of test is ArbinBT2000, the Autolab electrochemical workstation.
Measure conductivity
It is in 1.3 centimetres the kind cylindrical mold that the electrode composite material 1g of the lithium secondary battery of the present invention preparation is placed on diameter; With press it is pressed between the piston of two stainless steels; Pressure is 14MPa; Plate silver electrode after lamella taken out, and guarantee that any point-to-point transmission resistance on the same electrode slice after silver-plated is less than 10 -2Ohm.Carry out the measurement of conductivity with interchange composite impedance method well known by persons skilled in the art, use formula ρ=RS/L, obtain conductivity by resistance, wherein R is the resistance of measuring, and S is surface area 1.33cm 2, L is the thickness of lamella.Ionic conductivity is also used the ac impedance method of testing, wherein ionic diffusion coefficient D=R 2T 2/ 2A 2n 4F 4C 2V 2, Z Real=V ω -1/2
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The graphene powder that the present invention adopts can be for purchasing on the market.
Embodiment 1
LiFePO4/ Graphene/Li 3PO 4Preparation
(1) is raw material with ferrous oxalate, lithium carbonate and ammonium dihydrogen phosphate, is to take by weighing at 1.15: 1: 1.05 to be placed in the acetone soln by the mol ratio of Fe: Li: P, and adds the Graphene of 5wt%, make solid content reach 20%;
(2) material that step (1) is obtained mixes 20 hours to even in high energy ball mill, drum's speed of rotation is 500r/min, and the mass ratio of ball and grinding charge matter is 2: 1;
(3) drying of materials that adopts spray drying process that step (2) is obtained, the EAT of spray dryer is 220 ℃, leaving air temp is 100 ℃;
(4) mixture that step (3) is obtained places sintering furnace, after handling 10 hours under 650 ℃, is cooled to room temperature down in the nitrogen atmosphere protection, obtains required LiFePO4/ Graphene/Li 3PO 4Material, LiFePO4, Graphene and Li 3PO 4Mass ratio be 90: 5: 5.The performance of the electrode composite material of the lithium secondary battery of present embodiment preparation is as shown in table 1.
Embodiment 2
LiFePO 4The preparation of/Graphene/C
With LiFePO 4, Graphene and phenolic resins mixes, heat treatment under 400 ℃, nitrogen protection then obtains the electrode composite material of lithium secondary battery, said LiFePO 4The mass ratio of/Graphene/C is 97: 1: 2.The performance of the electrode composite material of the lithium secondary battery of present embodiment preparation is as shown in table 1.
Embodiment 3～10
Adopt the preparation method identical with embodiment 1, prepare the electrode composite material of lithium secondary battery, the raw material of the electrode composite material of said lithium secondary battery, performance etc. are as shown in table 1.
Respectively to electrode composite material, the LiFePO of the lithium secondary battery of embodiment 1～10 preparation 4, LiFePO 4/ C electrode composite material, LiFePO 4/ Graphene electrodes composite material carries out performance measurement, and the result is as shown in table 1.
The preparation raw material and the performance of table 1 polyanion material/Graphene/electric conducting material
Figure BDA0000048715000000141
Figure BDA0000048715000000151
On behalf of Graphene, C, G represent carbon, LFP to represent LiFePO4 in the accompanying drawing of the present invention.As shown in Figure 1, be followed successively by LiFePO among the figure from top to bottom 4, embodiment 2 preparation LiFePO 4/ Graphene/C and LiFe 0.99Mg 0.01PO 4/ Graphene/C/Li 3PO 4XRD figure.
Fig. 2, Fig. 3 are the LiFePO of embodiment 2 preparations 4The SEM photo of/Graphene/C.
Fig. 4 is LiFe in the table 1 0.99Mg 0.01PO 4/ Graphene/C/Li 3PO 4The TEM photo.
Fig. 5 is LiFePO 4LiFePO with embodiment 2 preparations 4The I-V performance plot of/Graphene/C.
Fig. 6 is LiFePO 4, LiFePO 4The LiFePO of/Graphene, embodiment 2 preparations 4/ Graphene/C and LiFe 0.99Mg 0.01PO 4/ Graphene/C/Li 3PO 4The charge-discharge performance curve.
Can obtain from The above results, the electrode composite material of the lithium secondary battery that the foregoing description prepares has electric conductivity preferably.、
Embodiment 11
LiMn 2O 4/ Graphene/Li 3PO 4Preparation
(1) with manganese dioxide, lithium carbonate raw material, Mn in molar ratio: Li=2: 1.05 ratio takes by weighing;
(2) mixture that step (1) is obtained mixes 7 hours to even in high energy ball mill, drum's speed of rotation is 500r/min, and the mass ratio of ball and grinding charge matter is 2: 1;
(3) in 100 ℃ of resistance-type heated ovens, heat 10 hours to dry;
(4) behind 850 ℃ of heat treatment 5h, be cooled to room temperature, obtain LiMn 2O 4
(5) with gained LiMn in the step (4) 2O 4With Graphene, LiOH and H 3PO 4Mix, wherein Graphene is LiMn 2O 46% of quality, LiOH and H 3PO 4Mol ratio be 3: 1, LiOH and H 3PO 4The quality sum be LiMn 2O 47.5% of quality, ground and mixed;
(6) step 5 gained mixture and the following 400 ℃ of heat treatments of nitrogen atmosphere were obtained LiMn in 1 hour 2O 4/ Graphene/Li 3PO 4
The performance of the electrode composite material of the lithium secondary battery of present embodiment preparation is as shown in table 2.
Embodiment 12
LiAl 0.02Mn 1.98O 4/ Graphene/Al 2O 3Preparation
With LiAl 0.02Mn 1.98O 4, Graphene and aluminum nitrate mix, heat treatment under 400 ℃, nitrogen protection then obtains the electrode composite material of lithium secondary battery, said LiAl 0.02Mn 1.98O 4/ Graphene/Al 2O 3Mass ratio be 97: 1: 2.The performance of the electrode composite material of the lithium secondary battery of present embodiment preparation is as shown in table 2.
Embodiment 13～18
Adopt the preparation method identical with embodiment 12, prepare the electrode composite material of lithium secondary battery, the raw material of the electrode composite material of said lithium secondary battery, performance etc. are as shown in table 2.
Respectively to electrode composite material, the LiMn of the lithium secondary battery of embodiment 11～18 preparation 2O 44, LiMn 2O 4/ Graphene electrodes composite material carries out performance measurement, and the result is as shown in table 1.
Table 2 contain lithium metal oxide/Graphene/electric conducting material preparation raw material and performance
Figure BDA0000048715000000171
Figure BDA0000048715000000181
As shown in Figure 7, be LiMn 2O 4And LiMn 2O 4The XRD figure of/Graphene.
Like Fig. 8, shown in Figure 9, be LiMn 2O 4With LiAl in the table 2 0.02Mn 1.98O 4/ Graphene/Li 3PO 4The SEM photo.
Figure 10 is LiMn 2O 4With LiAl in the table 2 0.02Mn 1.98O 4/ Graphene/Li 3PO 4Charging and discharging curve.
Can obtain from The above results, the electrode composite material of the lithium secondary battery that embodiment 11～18 prepares has electric conductivity preferably.
Embodiment 19
The preparation of silicon/Graphene/RESEARCH OF PYROCARBON material
(1) is that 10: 0.08: 0.1 tetraethoxysilane, Graphene, glucose is raw material with mass ratio, it is dissolved in the water that mass concentration is 30%;
(2) mixture that step (1) is obtained mixed in high energy ball mill 5 hours, and drum's speed of rotation is 500r/min, and the mass ratio of ball and grinding charge matter is 2: 1;
(3) adopt spray drying process that above-mentioned material is dry, the EAT of spray dryer is 220 ℃, and leaving air temp is 100 ℃;
(4) mixture that step (3) is obtained places atmosphere sintering furnace, exists down in the nitrogen atmosphere protection
Handle after 10 hours down for 900 ℃ and be cooled to room temperature, obtain silicon/Graphene/RESEARCH OF PYROCARBON material, the mass ratio of silicon/Graphene/RESEARCH OF PYROCARBON material is 90: 5: 5.The performance of the electrode composite material of the lithium secondary battery of present embodiment preparation is as shown in table 3.
Embodiment 20
The preparation of Si/ Graphene/C
Si, Graphene and glucose are mixed, and heat treatment under 400 ℃, nitrogen protection then obtains the electrode composite material of lithium secondary battery, and the mass ratio of said LSi/ Graphene/C is 90: 2: 8.The performance of the electrode composite material of the lithium secondary battery of present embodiment preparation is as shown in table 3.
Embodiment 21～25
Adopt the preparation method identical with embodiment 20, prepare the electrode composite material of lithium secondary battery, the electrode composite material raw material of said lithium secondary battery, performance etc. are as shown in table 3.
Respectively to electrode composite material, the LiMn of the lithium secondary battery of embodiment 19～25 preparation 2O 44, LiMn 2O 4/ Graphene electrodes composite material carries out performance measurement, and the result is as shown in table 1.
The preparation raw material and the performance of table 3 negative active core-shell material/Graphene/electric conducting material
Figure BDA0000048715000000191
Like Figure 11, Figure 12, Figure 13 and shown in Figure 14, be the SEM photo of the Si/ Graphene/C of embodiment 20 preparation.
Figure 15 is the charging and discharging curve of the Si/ Graphene/C of Si/C and embodiment 20 preparations.
Can obtain from The above results, the electrode composite material of the lithium secondary battery that embodiment 19～25 prepares has electric conductivity preferably.
The present invention provides electrode composite material of a kind of lithium secondary battery and preparation method thereof, and said electrode composite material comprises: lithium secondary battery electrode active material, Graphene and electric conducting material.Graphene and electric conducting material are distributed between surface of active material and active material particle, have formed the electrode composite material of said lithium secondary battery.Because Graphene has electron conduction preferably, therefore, has improved the electron conduction of electrode composite material.In addition, also comprise electric conducting material in the electrode composite material provided by the invention, thereby further improved the conductivity of electrode composite material with higher conductivity.Experimental result proves that the electronic conductivity of electrode composite material provided by the invention reaches 0.87S/cm, and ionic diffusion coefficient reaches 8.4 * 10 -8Cm 2/ S.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.

Claims (15)

1. the electrode composite material of a lithium secondary battery is characterized in that, comprising:
Lithium secondary battery electrode active material, Graphene and electric conducting material,
Said electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation mX n, conjugated structure conducting polymer and conductivity greater than 10 -10In the ionic conduction type material of S/cm one or more,
Wherein, X is O, S or N; M is Li, Na, one or more among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P; 0＜m＜10,0＜n＜10.
2. electrode composite material according to claim 1 is characterized in that, said ionic conduction type material is:
Contain lithium VI main group compound, contain VII main group compound, the LiTi of lithium 2(PO 4) 3, LiGe 2(PO 4) 3, Li pM rX q, contain the VI main group compound of lithium derivative, contain derivative, the LiTi of the VII main group compound of lithium 2(PO 4) 3Derivative, LiGe 2(PO 4) 3Derivative and Li pM rX qDerivative in one or more, M is one or more among P, C, the S, X is O and/or S, p, q and r are positive number.
3. electrode composite material according to claim 1 is characterized in that, the conducting polymer of said conjugated structure is polyaniline, polyacetylene, polypyrrole, polythiophene or polyphenylene sulfide.
4. electrode composite material according to claim 1 is characterized in that, the mass ratio of said lithium secondary battery electrode active material, Graphene and electric conducting material is 80～99: 0.01～10: 0.01～10.
5. electrode composite material according to claim 1; It is characterized in that; Said lithium secondary battery electrode active material is positive electrode active materials and/or negative active core-shell material; Said positive electrode active materials comprises polyanion material and the metal oxide that contains lithium, and said negative active core-shell material is that intermediate value discharges and recharges the active material of the potential difference of the relative lithium metal of current potential less than 2V.
6. electrode composite material according to claim 5 is characterized in that, said negative active core-shell material is a kind of in graphite, metal simple-substance, alloy, semimetal, metal oxide, metal nitride and the metal sulfide and several kinds.
7. electrode composite material according to claim 5, said polyanion material is a LiFePO4, and said metal oxide is a manganese Base Metal oxide, and said negative material is silicon, tin, Si oxide and/or tin-oxide.
8. electrode composite material according to claim 1 is characterized in that, said Graphene is that individual layer or the number of plies are that carbon atom is with sp between 1 to 20 layer, in the layer 2Hybridized orbit is formed hexagon honeycomb lattice, interlayer is the laminar material with carbon element that carbon atom combines with the π key; One or more grapheme material and/or intercalated graphite alkene in fluorine-containing, nitrogen, oxygen, carbonyl, carboxyl and the hydroxyl.
9. electrode composite material according to claim 1 is characterized in that, said lithium secondary battery electrode active material, Graphene and electric conducting material coexist with the form of mixing, compound, eutectic and/or physics contacts.
10. the preparation method of the electrode composite material of a lithium secondary battery is characterized in that, comprising:
Lithium secondary battery electrode active material or its presoma, Graphene, electric conducting material or its presoma are mixed, and heat treatment under 200～900 ℃, non-oxidizing atmosphere then obtains the electrode composite material of lithium secondary battery,
Said electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation mX n, conjugated structure conducting polymer and conductivity greater than 10 -10In the ionic conduction type material of S/cm one or more,
Wherein, X is O, S or N; M is Li, Na, one or more among K, Mg, Ca, AL, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Si, Pb, In, Y, the P; 0＜m＜10,0＜n＜10.
11. preparation method according to claim 10 is characterized in that, said ionic conduction type material is:
Contain lithium VI main group compound, contain VII main group compound, the LiTi of lithium 2(PO 4) 3, LiGe 2(PO 4) 3, Li pM rX q, contain the VI main group compound of lithium derivative, contain derivative, the LiTi of the VII main group compound of lithium 2(PO 4) 3Derivative, LiGe 2(PO 4) 3Derivative and Li pM rX qDerivative in one or more, M is one or more among P, C, the S, X is O and/or S, p, q and r are positive number.
12. preparation method according to claim 10 is characterized in that, the mass ratio of said lithium secondary battery electrode active material, Graphene and electric conducting material is 80～99: 0.01～10: 0.01: 10.
13. preparation method according to claim 10; It is characterized in that; Said lithium secondary battery electrode active material comprises positive electrode active materials and/or negative active core-shell material; Said positive electrode active materials comprises polyanion material and the metal oxide that contains lithium, and said negative material is that intermediate value discharges and recharges the active material of the potential difference of the relative lithium metal of current potential less than 2V.
14. preparation method according to claim 10 is characterized in that, said Graphene is that individual layer or the number of plies are that carbon atom is with sp between 1 to 20 layer, in the layer 2Hybridized orbit is formed hexagon honeycomb lattice, and interlayer is the laminar material with carbon element that carbon atom combines with the π key; One or more grapheme material and/or intercalated graphite alkene in fluorine-containing, nitrogen, oxygen, carbonyl, carboxyl and the hydroxyl.
15. preparation method according to claim 10 is characterized in that, said heat treatment time is 0.2～50 hour.
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