CN102420323B - 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 PDFInfo
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- CN102420323B CN102420323B CN201110051233.0A CN201110051233A CN102420323B CN 102420323 B CN102420323 B CN 102420323B CN 201110051233 A CN201110051233 A CN 201110051233A CN 102420323 B CN102420323 B CN 102420323B
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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
Technical field
The present invention relates to 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 day by day exhausted and global warming of resource, the life style of green low-carbon has been subject to advocating.Wherein, to come part to replace the internal-combustion engines vehicle of consumption of fossil fuels be one of main method solving energy crisis and ecological deterioration to development electric motor car and hybrid electric vehicle.Driving power is to affect 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.In various driving powers, lithium secondary battery is high owing to having energy density, and cyclicity is good, and self-discharge rate is low, long service life and the advantage such as environmental pressure is little, has obtained research widely.
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 current lithium secondary battery; Metal and alloy thereof, such as Li metal and alloy, Ni sill and Zn sill etc., are the negative materials being used the earliest in lithium secondary battery; Semi-metallic is enhanced than the specific capacity of graphite, to improving the specific energy of secondary cell, has important strategic importance; Metal oxide, metal nitride, metal sulfide can be expressed as M
mx
nwherein X is O, S, or N, M is selected from Li, Na, one or more in 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, P, 0 < m < 10,0 < n < 10, and between M, X, m, n, carry out Selection and Constitute 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 containing lithium.Conventional comprises cobalt acid lithium, LiMn2O4, rich lithium stratiform nickel LiMn2O4 and lithium nickelate etc. containing lithium metal oxide, 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, containing the metal oxide of lithium when high current charge-discharge, easily there is safety problem, now need to adopt some to there is 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 one metal wherein can be oxidizing to higher valence state, comprises at least one in iron, aluminium, titanium, cobalt, boron, chromium, nickel, magnesium, zirconium, gallium, vanadium, manganese and 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 in alkali metal ion, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn and Pb, 0≤b '≤5; At X
cy
din, X is selected from one or more in P, As, Sb, Si, Ge, V, S, and Y is selected from one or more in S, O, N, 0 < c≤5,0 < d≤10; Z is option, comprises OH, one or more in halogen, N, S, 0 < f≤10; Wherein, to A, M, M ', X, Y, Z, a, b, b ', c, d, e, f selects to keep compound to be electric neutrality.Owing to containing polyanion in polyanion material, therefore there is 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 lithium metal ion, cause the electric conductivity of this material poor, be difficult to carry out high current charge-discharge, therefore need to as added electronic conductive material and/or ion conductive material, improve by variety of way the high rate performance of this material.
In the Chinese patent literature that is CN101453020A at publication number, the M A Ermeng of Quebec, CAN water power company proposes to use the coated polyanion material of RESEARCH OF PYROCARBON, makes the conductivity of material reach 10
-8s/cm; In patent CN1652999A, the people such as Jeremy's Bark of Willens Technologies, Inc. propose to use carbon thermal reduction to prepare polyanion material, improved to a certain extent the conductivity of polyanion material, but, it is unsatisfactory that this polyanion material obtains electric conductivity, former because while preparing polyanion material, for fear of polyanion material, will undergo phase transition, the heat treatment temperature of using is generally 600～750 ℃, but, when heat treatment temperature is 750 degree when following, determine the Sp of the electric conductivity of RESEARCH OF PYROCARBON material
2the degree of graphitization of hydridization is conventionally lower.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 that a class has individual layer or which floor sp of minority
2the lonsdaleite material of hydridization, in sandwich construction, interlayer is with the combination of π key form, and because this electron-like is diracelectron near Fermi's energy, effective mass is zero, so conductivity reaches 10
6s/cm is the highest material of electric conductivity that the current mankind find.Application number be 200910155316.7 and the application number Chinese patent literature that is 201010226062.6 in, the Liu Zhao equality of Ningbo Material Technology and Engineering Inst. of the Chinese Academy of Sciences proposes to use Graphene and polyanion Material cladding, has 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 invention provides the electrode composite material that the technical problem that will solve is to provide a kind of lithium secondary battery, this composite material has higher electric conductivity.
The electrode composite material that the invention provides a kind of lithium secondary battery, comprising:
Lithium secondary battery electrode active material, Graphene and electric conducting material,
Described electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation
mx
n, conjugated structure conducting polymer and conductivity be greater than 10
-10one or more in the ionic conduction shaped material of S/cm,
Wherein, X is O, S or N, M is Li, Na, one or more in 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, P, 0 < m < 10,0 < n < 10.
Preferably, described ionic conduction shaped material is:
Containing the VI main group compound of lithium, containing VII main group compound, the LiTi of lithium
2(PO
4)
3, LiGe
2(PO
4)
3, Li
pm
rx
q, containing the derivative of the VI main group compound of lithium, containing 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 in P, C, S, X is O and/or S, p, q and r are positive number.
Preferably, the conducting polymer of described conjugated structure is polyaniline, polyacetylene, polypyrrole, polythiophene or polyphenylene sulfide.
Preferably, the mass ratio of described lithium secondary battery electrode active material, Graphene and electric conducting material is 80～99: 0.01～10: 0.01～10.
Preferably, described lithium secondary battery electrode active material is positive electrode active materials and/or negative active core-shell material, described positive electrode active materials comprises polyanion material and containing the metal oxide of lithium, described negative active core-shell material is the active material that the potential difference of the relative lithium metal of intermediate value charge and discharge potential is less than 2V.
Preferably, described negative active core-shell material is a kind of and several in graphite, metal simple-substance, alloy, semimetal, metal oxide, metal nitride and metal sulfide.
Preferably, described polyanion material is LiFePO4, and described metal oxide is manganese Base Metal oxide, and described negative material is silicon, tin, Si oxide and/or tin-oxide.
Preferably, described Graphene is that individual layer or the number of plies are that carbon atom is with sp between 1 to 20 layer, in layer
2hybridized orbit forms hexagon honeycomb lattice, interlayer is the laminar material with carbon element that carbon atom closes with π bond; One or more grapheme material and/or intercalated graphite alkene in fluorine-containing, nitrogen, oxygen, carbonyl, carboxyl and hydroxyl.
Preferably, described lithium secondary battery electrode active material, Graphene and electric conducting material mixing, the form of compound, eutectic and/or physical contact coexists.
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 then heat treatment under 200～900 ℃, non-oxidizing atmosphere, obtains the electrode composite material of lithium secondary battery,
Described electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation
mx
n, conjugated structure conducting polymer and conductivity be greater than 10
-10one or more in the ionic conduction shaped material of S/cm,
Wherein, X is O, S or N, M is Li, Na, one or more in 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, P, 0 < m < 10,0 < n < 10.
Preferably, described ionic conduction shaped material is:
Containing the VI main group compound of lithium, containing VII main group compound, the LiTi of lithium
2(PO
4)
3, LiGe
2(PO
4)
3, Li
pm
rx
q, containing the derivative of the VI main group compound of lithium, containing 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 in P, C, S, X is O and/or S, p, q and r are positive number.
Preferably, the mass ratio of described lithium secondary battery electrode active material, Graphene and electric conducting material is 80～99: 0.01～10: 0.01: 10.
Preferably, described lithium secondary battery electrode active material comprises positive electrode active materials and/or negative active core-shell material, described positive electrode active materials comprises polyanion material and containing the metal oxide of lithium, described negative material is the active material that the potential difference of the relative lithium metal of intermediate value charge and discharge potential is less than 2V.
Preferably, described Graphene is that individual layer or the number of plies are that carbon atom is with sp between 1 to 20 layer, in layer
2hybridized orbit forms hexagon honeycomb lattice, and interlayer is the laminar material with carbon element that carbon atom closes with π bond; One or more grapheme material and/or intercalated graphite alkene in fluorine-containing, nitrogen, oxygen, carbonyl, carboxyl and hydroxyl.
Preferably, described heat treatment time is 0.2～50 hour.
From above-mentioned technical scheme, can find out, the invention provides electrode composite material of a kind of lithium secondary battery and preparation method thereof, described 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 described lithium secondary battery.Because Graphene has good electron conduction, therefore, improved the electron conduction of electrode composite material.In addition, in electrode composite material provided by the invention, also comprise the electric conducting material with higher conductivity, thereby further improved the conductivity of electrode composite material.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 conductivity.The results show, 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.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is LiFePO
4, the embodiment of the present 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 present invention 2 preparations
4the SEM photo of/Graphene/C;
Fig. 3 is the LiFePO of the embodiment of the present invention 2 preparations
4the SEM photo of/Graphene/C;
Fig. 4 is LiFe prepared by the embodiment of the present invention
0.99mg
0.01pO
4/ Graphene/C/Li
3pO
4tEM photo;
Fig. 5 is LiFePO
4liFePO with the embodiment of the present 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 present invention 2 preparations
4liFe prepared by/Graphene/C and the embodiment of the present invention
0.99mg
0.01pO
4/ Graphene/C/Li
3pO
4charge-discharge performance curve;
Fig. 7 is LiMn
2o
4and LiMn
2o
4the XRD figure of/Graphene;
Fig. 8 is LiMn
2o
4the LiAl preparing with the embodiment of the present invention
0.02mn
1.98o
4/ Graphene/Li
3pO
4sEM photo;
Fig. 9 is LiMn
2o
4the LiAl preparing with the embodiment of the present invention
0.02mn
1.98o
4/ Graphene/Li
3pO
4sEM photo;
Figure 10 is LiMn
2o
4the LiAl preparing with the embodiment of the present invention
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 present invention 20 preparations;
Figure 12 is the SEM photo of the Si/ Graphene/C of the embodiment of the present invention 20 preparations;
Figure 13 is the SEM photo of the Si/ Graphene/C of the embodiment of the present invention 20 preparations;
Figure 14 is the SEM photo of the Si/ Graphene/C of the embodiment of the present invention 20 preparations;
Figure 15 is the charging and discharging curve of the Si/ Graphene/C of Si/C and the embodiment of the present invention 20 preparations.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The electrode composite material that the embodiment of the invention discloses a kind of lithium secondary battery, comprising:
Lithium secondary battery electrode active material, Graphene and electric conducting material,
Described electric conducting material be the oxide of graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, conductive carbon material, Ag, Cu, Pt, Au, Ag, the oxide of the oxide of Cu, Pt, the sulfide of the oxide of Au, Ag, the sulfide of the sulfide of Cu, Pt, the nitride of the sulfide of Au, Ag, the nitride of the nitride of Cu, Pt, the nitride of Au, organic conductive material and conductivity are greater than 10
-8one or more in the ionic conduction shaped material of S/cm.
Described lithium secondary battery electrode active material preferably includes positive electrode active materials and/or negative active core-shell material, described positive electrode active materials comprises polyanion material and containing the metal oxide of lithium, and the potential difference that described negative active core-shell material is preferably the relative lithium metal of intermediate value charge and discharge potential is less than the active material of 2V.
In the present invention, described polyanion material is 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 one metal wherein can be oxidizing to higher valence state, comprises at least one in iron, aluminium, titanium, cobalt, boron, chromium, nickel, magnesium, zirconium, gallium, vanadium, manganese and 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 in alkali metal ion, Ti, Sc, Ge, V, Cr, Zr, Co, Ni, Zn, Cu, Mn, Hf, Nb, Ta, Mo, W, Ru, Ag, Sn, Pb, 0≤b '≤5; X
cy
din, wherein X is selected from one or more in P, As, Sb, Si, Ge, V, S, and Y is selected from one or more in S, O, N, 0 < c≤5,0 < d≤10; Z is option, comprises OH, one or more in halogen, N, S, 0 < f≤10; Wherein, to A, M, M ', X, Y, Z, a, b, b ', c, d, e, f selects to keep compound to be electric neutrality.
It is A that the above-mentioned metal oxide containing 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, 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 in halogen, N, S, and the metal oxide of described 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.
The potential difference that above-mentioned negative active core-shell material is preferably the relative lithium metal of intermediate value charge and discharge potential is less than the active material of 2V, be preferably a kind of and several in graphite, metal simple-substance, alloy, semimetal, metal oxide, metal nitride and metal sulfide, specifically comprise lithium metal, material with carbon element, can form with lithium material, metal oxide, metal sulfide of alloy etc.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.The described material that can form alloy with lithium can be metallic element, and such as Mg, B, Al, Ga, In, Si, Sn, Pb, Sb, Bi, Cd, Ag, Zn, Hf, Zr, Y etc., for example, containing the alloy of Si and Sn, 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, as SiC, Si
3n
4, Si
2n
2o, Ge
2n
2o, SiO
x(0 < x≤2), SnO
x(0 < x≤2), LiSiO and LiSnO etc.Described metal oxide, metal sulfide can be expressed as M
mx
n(X=O, S, or N), comprises and can be expressed as M
mx
n(X=O, S, or N), wherein M is selected from Li, Na, one or more in 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, P, 0 < m < 10,0 < n < 10, and between M, X, m, n, carry out Selection and Constitute to guarantee M
mx
nbe electric neutrality, especially comprise SnO, SnO
2, SiO
2the compound of sill, oxide and metal, as Si/SiO
2compound, Sn/SnO, Sn/SnO
2.
Graphene is that a class has individual layer or which floor sp of minority
2the lonsdaleite material of hydridization, in sandwich construction, interlayer is with the combination of π key form, and because this electron-like is diracelectron near Fermi's energy, effective mass is zero, so conductivity reaches 10
6s/cm is the highest material of electric conductivity that the current mankind find.Described Graphene is that individual layer or the number of plies are between 1 to 20 layer, in layer, is that carbon atom is with Sp
2hybridized orbit forms hexagon honeycomb lattice, the laminar material with carbon element that interlayer closes with π bond.In addition, that the present invention has also comprised is fluorine-containing, one or more grapheme material and intercalated graphite alkene etc. in nitrogen, oxygen, carbonyl, carboxyl, hydroxyl, and the grapheme material that comprises inevitable defect.
Electric conducting material described in the present invention is preferably electron conductive type or the ionic conduction shaped material except Graphene, and the equal material preferably of electron conduction and ionic conductivity.Described electronic conductive material is specially conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation
mx
n, conjugated structure conducting polymer and conductivity be greater than 10
-10one or more in the ionic conduction shaped material of S/cm, wherein, X is O, S or N, M is Li, Na, one or more in 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, P, 0 < m < 10,0 < n < 10, and between M, X, m, n, carry out Selection and Constitute to guarantee M
mx
nbe electric neutrality.Described semimetal is preferably Si or Ge, and the conducting polymer of described conjugated structure is preferably one or more in polyaniline, polyacetylene, polypyrrole, polythiophene and polyphenylene sulfide.
Described ionic conduction shaped 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, containing the derivative of the VI main group compound of lithium, containing 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 in P, C, S, X is O and/or S, p, q and r are positive number.
The mass ratio of described 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 coexist formal distribution between surface of active material and active material particle by one or more ways of contact of even mixing, compound, parcel, eutectic, physical contact.Because Graphene has good electron conduction, therefore, improved the electron conduction of electrode composite material.In addition, in electrode composite material provided by the invention, also comprise the electric conducting material with higher conductivity, thereby further improved the conductivity of electrode composite material.
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 then heat treatment under 200～900 ℃, non-oxidizing atmosphere, obtains the electrode composite material of lithium secondary battery,
Described electric conducting material is conductive carbon material, Ag, Cu, Pt, Au, magnesium-yttrium-transition metal, semimetal, the M of graphite, expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, organic matter pyrolysis generation
mx
n, conjugated structure conducting polymer and conductivity be greater than 10
-10one or more in the ionic conduction shaped material of S/cm,
Wherein, X is O, S or N, M is Li, Na, one or more in 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, P, 0 < m < 10,0 < n < 10.
Lithium secondary battery electrode active material precursor compound of the present invention and electric conducting material precursor compound are precursor compound as known in the art.
Described lithium secondary battery electrode active material comprises positive electrode active materials and/or negative active core-shell material, described positive electrode active materials comprises polyanion material and containing the metal oxide of lithium, described negative material is the active material that the potential difference of the relative lithium metal of intermediate value charge and discharge potential is less than 2V.
Described ionic conduction shaped 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, containing the derivative of the VI main group compound of lithium, containing 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 in P, C, S, X is O and/or S, p, q and r are positive number.
The mass ratio of described 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.
Described non-oxygen atmosphere is preferably one or more in argon gas, nitrogen, hydrogen, carbon monoxide and carbon dioxide.Described heat treatment temperature is preferably 300～800 ℃, more preferably 400～700 ℃.Described 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 simple physical mixed, and such as ball milling, grinding, Ultrafine Grinding, be uniformly mixed etc., described hybrid mode also preferably includes molecular level mixes, such as mixing after dissolving etc.
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 preparing, for example, preferably adopt that spraying is dry, the method preparation of precipitation, co-precipitation, reunion and/or granulation.When adopting spraying dry, the electrode composite material of the lithium secondary battery preparing be shaped as spherical agglomerates, it is of a size of 0.5～50 micron, each aggregate is comprised of less particle.
In the process of electrode composite material of preparing described lithium secondary battery, preferably in the reactor of promotion pressed powder balance, carry out, for example be selected from following reactor: the converter that fluid bed, converter, pusher furnace, belt drive, described reactor can be controlled the composition of gas atmosphere and flow.
Electric conducting material of the present invention is 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 surface of active material original position.The RESEARCH OF PYROCARBON material that its situ produces can improve the conductivity on active material particle surface, Graphene is for improving the conductivity between particle simultaneously, therefore adopt Graphene and two kinds of electric conducting materials of RESEARCH OF PYROCARBON material, its conduction effect can be better than 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 shaped material of S/cm.Because ionic conduction shaped material has the effect of the ionic conductivity that improves active material interface, Graphene is for improving the conductivity between particle simultaneously, and the conductivity of the electrode composite material of the lithium secondary battery therefore being formed by lithium secondary battery electrode active material, Graphene and ionic conduction shaped material is good.
The active material of lithium secondary battery electrode described in the present invention, electric conducting material are purchased from the 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 be prepared.
The preparation method of the polyanionic compound in lithium secondary battery electrode active material of the present invention preferably adopts with the following method:
(1) choose containing the transition metal ions compound, lithium salts and the polyanionic salt raw material that appraise at the current rate, by stoichiometric proportion, take and be placed in acetone dispersant, make solid content reach 10%-70%;
(2) in high energy ball mill, mix 1～20 hour to after evenly, dry;
(3) mixture in (2) is placed in to atmosphere sintering furnace, is cooled to room temperature process 1h～48 hour at 200～800 ℃ under non-oxidizing atmosphere protection after, obtain required polyanion material;
(4) test this material electrochemical performance and conductivity.
Described lithium salts preferably includes lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium bromide, lithium fluoride, lithium nitride, containing one or more combination of the lithium salts of polyanion.Transition metal ions compound comprises transition metal oxide, sulfate, phosphate, nitrate, oxalates, acetate, citrate, containing one or more the combination in the slaine of polyanion.Polyanionic salt preferably includes acid containing polyanion, ammonium salt, ester class, hydro carbons, containing one or more combination of the slaine of polyanion.Wherein lithium, containing the metal ions M of appraising at the current rate, the mol ratio of polyanion, be the content of demarcating in chemical formula, domain of walker is 80% to 120% of metering ratio;
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%, preferably 20%～40%.The dry means of direct drying or vacuum filtration that adopt of spraying are carried out.Above-mentioned heat treatment time can be preferably 1～48 hour heating time between 200～1000 ℃, and preferably temperature is 600～800 ℃, and be preferably 3～15 hours heating time.
Metal oxide in lithium secondary battery electrode active material of the present invention, with LiMn
2o
4for the preparation method of example as follows:
(1) choosing the ratio that manganese dioxide, lithium carbonate raw material, in molar ratio Mn: Li are 2: 1.05 takes;
(2) mixture step (1) being obtained mixes 7 hours to after evenly in high energy ball mill, adds dispersant in process of lapping, dry;
(3) product step (2) being obtained is cooled to room temperature after 850 ℃ of heat treatment 5h, obtains required lithium manganate material, and resulting materials is pure phase LiMn
2o
4.
When electro-chemical test shows to discharge and recharge under 20mA/g current density, the capacity of this material is 110mAh/g, and the conductivity of material is 5.1X10
-4s/cm.
When lithium secondary battery electrode active material of the present invention is negative active core-shell material, silica/graphene/carbon material of take is example, and preparation method is preferably:
Step (1) is by the compound of silicon, containing carbon compound and Graphene, in ball mill, fully mix, add 30wt% grinding aid acetone simultaneously, wherein Graphene is composition quality 1%～5%, silica is 50%～90% of composition quality, material with carbon element quality and be 3%～50% of composition quality;
Step (2) is by step (1) gained mixture under nitrogen atmosphere protection, and in vacuum furnace, 200 ℃～1000 ℃ heat treatment is 1～20 hour, thereby obtains end-product silica/graphene/carbon material compositions.
Described material with carbon element can improve the nanometer degree of the electrode composite material of lithium secondary battery, suppresses the change in volume in electrochemical process, and improves conductivity.Graphene can further improve 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 cladding silicium cathode material, can improve the conductivity of negative active core-shell material, suppress the change in volume in charge and discharge process, thereby reach raising specific capacity, improve the effect of cycle life.The cost of the electrode composite material of the lithium secondary battery therefore, preparing.
The electrode composite material of lithium secondary battery provided by the invention of take is 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.
Described barrier film is preferably the macromolecule membrane of porous, as microporous polypropylene film etc.Described nonaqueous electrolytic solution consists of nonaqueous solvents and electrolyte.Described 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 propionic ester etc.Electrolyte is preferably salt containing lithium, as 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 chemical property and the conductivity of the electrode composite material of lithium secondary battery prepared by the present invention.
Test chemical property
The electrode composite material of lithium secondary battery prepared by the present invention, Kynoar (PVDF), conductive acetylene is black is to join in 1-METHYLPYRROLIDONE at 80: 5: 15 in mass ratio, after magnetic agitation is even, positive plate is made in oven dry, and with glove box in be assembled into 2032 button cells, wherein negative pole is lithium sheet, barrier film is 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, Autolab electrochemical workstation.
Measure conductivity
It is in the kind cylindrical mold of 1.3 centimetres that the electrode composite material 1g of lithium secondary battery prepared by the present invention is placed on diameter, with press, be pressed between the piston of two stainless steels, pressure is 14MPa, after will lamella taking out, plate silver electrode, and guarantee that between any two points on the same electrode slice after silver-plated, resistance is less than 10
-2ohm.By interchange composite impedance method well known by persons skilled in the art, carry out the measurement of conductivity, use formula ρ=RS/L, by resistance, obtain conductivity, 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 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 illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The graphene powder that the present invention adopts can be for purchasing on market.
Embodiment 1
LiFePO4/ Graphene/Li
3pO
4preparation
(1) take ferrous oxalate, lithium carbonate and ammonium dihydrogen phosphate as raw material, by the mol ratio of Fe: Li: P, be to take at 1.15: 1: 1.05 to be placed in acetone soln, and add the Graphene of 5wt%, make solid content reach 20%;
(2) material step (1) being obtained mixes 20 hours to even in high energy ball mill, and drum's speed of rotation is 500r/min, and ball is 2: 1 with the mass ratio that is polished material;
(3) material that adopts spray drying process that step (2) is obtained is dry, and the inlet temperature of spray dryer is 220 ℃, and leaving air temp is 100 ℃;
(4) mixture step (3) being obtained is placed in sintering furnace, is cooled to room temperature after processing 10 hours under nitrogen atmosphere protection at 650 ℃, 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 lithium secondary battery prepared by the present embodiment is as shown in table 1.
LiFePO
4the preparation of/Graphene/C
By LiFePO
4, Graphene and phenolic resins mixes, then heat treatment under 400 ℃, nitrogen protection, obtains the electrode composite material of lithium secondary battery, described LiFePO
4the mass ratio of/Graphene/C is 97: 1: 2.The performance of the electrode composite material of lithium secondary battery prepared by the present embodiment is as shown in table 1.
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 described lithium secondary battery, performance etc. are as shown in table 1.
Electrode composite material, the LiFePO of the lithium secondary battery of respectively being prepared by embodiment 1～10
4, LiFePO
4/ C electrode composite material, LiFePO
4/ Graphene electrodes composite material carries out performance measurement, and result is as shown in table 1.
Raw materials and the performance of table 1 polyanion material/Graphene/electric conducting material
In accompanying drawing of the present invention, G represents that Graphene, C represent that carbon, LFP represent LiFePO4.As shown in Figure 1, in figure, be followed successively by from top to bottom LiFePO
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 table 1
0.99mg
0.01pO
4/ Graphene/C/Li
3pO
4tEM 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
4charge-discharge performance curve.
From the above results, can obtain, the electrode composite material of the lithium secondary battery that above-described embodiment prepares has good electric conductivity.、
Embodiment 11
LiMn
2o
4/ Graphene/Li
3pO
4preparation
(1) with manganese dioxide, lithium carbonate raw material, in molar ratio Mn: Li=2: 1.05 ratio takes;
(2) mixture step (1) being obtained mixes 7 hours to even in high energy ball mill, and drum's speed of rotation is 500r/min, and ball is 2: 1 with the mass ratio that is polished material;
(3) in 100 ℃ of resistance-type heated ovens, heat 10 hours to dry;
(4) after 850 ℃ of heat treatment 5h, be cooled to room temperature, obtain LiMn
2o
4;
(5) by gained LiMn in 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
4quality sum be LiMn
2o
47.5% of quality, ground and mixed;
(6) step 5 gained mixture and the lower 400 ℃ of heat treatments of nitrogen atmosphere are obtained to LiMn for 1 hour
2o
4/ Graphene/Li
3pO
4.
The performance of the electrode composite material of lithium secondary battery prepared by the present embodiment is as shown in table 2.
Embodiment 12
LiAl
0.02mn
1.98o
4/ Graphene/Al
2o
3preparation
By LiAl
0.02mn
1.98o
4, Graphene and aluminum nitrate mix, then heat treatment under 400 ℃, nitrogen protection, obtains the electrode composite material of lithium secondary battery, described LiAl
0.02mn
1.98o
4/ Graphene/Al
2o
3mass ratio be 97: 1: 2.The performance of the electrode composite material of lithium secondary battery prepared by the present embodiment 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 described lithium secondary battery, performance etc. are as shown in table 2.
Electrode composite material, the LiMn of the lithium secondary battery of respectively being prepared by embodiment 11～18
2o
44, LiMn
2o
4/ Graphene electrodes composite material carries out performance measurement, and result is as shown in table 1.
Table 2 containing the metal oxide/Graphene/electric conducting material of lithium raw materials and performance
As shown in Figure 7, be LiMn
2o
4and LiMn
2o
4the XRD figure of/Graphene.
As shown in Figure 8, Figure 9, be LiMn
2o
4with LiAl in table 2
0.02mn
1.98o
4/ Graphene/Li
3pO
4sEM photo.
Figure 10 is LiMn
2o
4with LiAl in table 2
0.02mn
1.98o
4/ Graphene/Li
3pO
4charging and discharging curve.
From the above results, can obtain, the electrode composite material of the lithium secondary battery that embodiment 11～18 prepares has good electric conductivity.
The preparation of silicon/Graphene/RESEARCH OF PYROCARBON material
(1) take tetraethoxysilane, Graphene, the glucose that mass ratio is 10: 0.08: 0.1 is raw material, is dissolved in water, and mass concentration is 30%;
(2) mixture step (1) being obtained mixes 5 hours in high energy ball mill, and drum's speed of rotation is 500r/min, and ball is 2: 1 with the mass ratio that is polished material;
(3) adopt spray drying process that above-mentioned material is dry, the inlet temperature of spray dryer is 220 ℃, and leaving air temp is 100 ℃;
(4) mixture step (3) being obtained is placed in atmosphere sintering furnace, under nitrogen atmosphere protection
At 900 ℃, process after 10 hours 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 lithium secondary battery prepared by the present embodiment is as shown in table 3.
The preparation of Si/ Graphene/C
Si, Graphene and glucose are mixed, and then heat treatment under 400 ℃, nitrogen protection, obtains the electrode composite material of lithium secondary battery, and the mass ratio of described LSi/ Graphene/C is 90: 2: 8.The performance of the electrode composite material of lithium secondary battery prepared by the present embodiment 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 described lithium secondary battery, performance etc. are as shown in table 3.
Electrode composite material, the LiMn of the lithium secondary battery of respectively being prepared by embodiment 19～25
2o
44, LiMn
2o
4/ Graphene electrodes composite material carries out performance measurement, and result is as shown in table 1.
The raw materials of table 3 negative active core-shell material/Graphene/electric conducting material and performance
As shown in Figure 11, Figure 12, Figure 13 and Figure 14, it is 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.
From the above results, can obtain, the electrode composite material of the lithium secondary battery that embodiment 19～25 prepares has good electric conductivity.
The invention provides electrode composite material of a kind of lithium secondary battery and preparation method thereof, described 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 described lithium secondary battery.Because Graphene has good electron conduction, therefore, improved the electron conduction of electrode composite material.In addition, in electrode composite material provided by the invention, also comprise the electric conducting material with higher conductivity, thereby further improved the conductivity of electrode composite material.The results show, 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.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (1)
1. an electrode composite material for lithium secondary battery, is characterized in that, in accordance with the following methods preparation:
With iron oxide, vanadium oxide, lithium carbonate, ammonium dihydrogen phosphate, PEG, LiOH, H
3pO
4for raw material, take and be placed in acetone soln, and add the Graphene of 5wt%, make solid content reach 20%;
The material that above-mentioned steps is obtained mixes 20 hours to even in high energy ball mill, and drum's speed of rotation is 500r/min, and ball is 2:1 with the mass ratio that is polished material;
The material that adopts spray drying process that above-mentioned steps is obtained is dry, and the inlet temperature of spray dryer is 220 ℃, and leaving air temp is 100 ℃;
The mixture that above-mentioned steps is obtained is placed in sintering furnace, is cooled to room temperature after processing 10 hours under nitrogen atmosphere protection at 650 ℃, obtains required LiFe
0.99v
0.01pO
4/ Graphene/C/Li
3pO
4, LiFe
0.99v
0.01pO
4, Graphene, C and Li
3pO
4mass ratio be 95:1:1:3;
Or preparation in accordance with the following methods:
With iron oxide, vanadium oxide, magnesium oxide, lithium carbonate, phosphoric acid, PEG, PVA, LiOH, H
3pO
4for raw material, take and be placed in acetone soln, and add the Graphene of 5wt%, make solid content reach 20%;
The material that above-mentioned steps is obtained mixes 20 hours to even in high energy ball mill, and drum's speed of rotation is 500r/min, and ball is 2:1 with the mass ratio that is polished material;
The material that adopts spray drying process that above-mentioned steps is obtained is dry, and the inlet temperature of spray dryer is 220 ℃, and leaving air temp is 100 ℃;
The mixture that above-mentioned steps is obtained is placed in sintering furnace, is cooled to room temperature after processing 10 hours under nitrogen atmosphere protection at 650 ℃, obtains required LiFe
0.98v
0.01mg
0.01pO
4/ Graphene/C/Li
3pO
4, LiFe
0.98v
0.01mg
0.01pO
4, Graphene, C and Li
3pO
4mass ratio be 95:1:1:3;
Or preparation in accordance with the following methods:
With manganese nitrate, chromic nitrate, lithium carbonate, phosphoric acid, AgNO
3, PVA, butyl titanate, H
3pO
4for raw material, take and be placed in acetone soln, and add the Graphene of 5wt%, make solid content reach 20%;
The material that above-mentioned steps is obtained mixes 20 hours to even in high energy ball mill, and drum's speed of rotation is 500r/min, and ball is 2:1 with the mass ratio that is polished material;
The material that adopts spray drying process that above-mentioned steps is obtained is dry, and the inlet temperature of spray dryer is 220 ℃, and leaving air temp is 100 ℃;
The mixture that above-mentioned steps is obtained is placed in sintering furnace, is cooled to room temperature after processing 10 hours under nitrogen atmosphere protection at 650 ℃, obtains required LiMn
0.99cr
0.01pO
4/ Graphene/Ag/C/LiTi
2(PO
4)
3, LiMn
0.99cr
0.01pO
4, Graphene, Ag and C/LiTi
2(PO
4)
3mass ratio be 95:1:1:2.
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