CN101740750B - Method for preparing anode active substance, anode active substance, anode and battery - Google Patents
Method for preparing anode active substance, anode active substance, anode and battery Download PDFInfo
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- CN101740750B CN101740750B CN2008101892354A CN200810189235A CN101740750B CN 101740750 B CN101740750 B CN 101740750B CN 2008101892354 A CN2008101892354 A CN 2008101892354A CN 200810189235 A CN200810189235 A CN 200810189235A CN 101740750 B CN101740750 B CN 101740750B
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Abstract
The invention provides a method for preparing an anode active substance, the anode active substance prepared by the method, an anode comprising the anode active substance and a battery comprising the anode. The method for preparing the anode active substance comprises the step of sintering a mixture which comprises a raw material 1 and a raw material 2; the raw material 1 is one or more of compounds represented by general formulas: LixM'y(XO4)z, LiM'XO5, LiM'XO6 and LiM'X2O7, wherein x/z is more than 0 and less than or equal to 1, y/z is more than 0 and less than or equal to 1.1, M' is one or more of Na, Mn, Fe, Co, Ni, Ti, V, Y, Mg, Ca and Zn, and X is P, S, As, Mo or W; and the raw material 2 is one or more of compounds represented by a general formula: AaMbNcOd, wherein A, M, and N are different from one another, and are IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII group metallic elements respectively, and a and b are not simultaneously 0. The anode active substance prepared by the method can obviously improve the specific capacity of quality and cycle performance of the battery.
Description
Technical field
The invention relates to a kind of preparation method of positive active material and the positive active material that is made by this preparation method and the positive pole that comprises this positive active material and comprise the battery that this is anodal, positive active material and the positive pole that comprises this positive active material that especially makes about a kind of preparation method of positive active material of lithium secondary battery and by this preparation method and comprise the battery that this is anodal.
Background technology
Lithium secondary battery also is the first-selected power supply of following electric automobile and hybrid-electric car because of the ideal source that it has that specific energy is large, self discharge is little, has extended cycle life, lightweight and advantages of environment protection becomes portable type electronic product.Therefore lithium secondary battery and associated materials thereof have become one of study hotspot of countries in the world scientific research personnel.Wherein positive active material owing on the high side, specific capacity is on the low side become the restriction lithium secondary battery by the bottleneck of large-scale application.At present the inorganic metal compound material is by the metal sulfide of the first generation, develop into the metal oxide of the second generation, but above-mentioned two classes have the shortcoming that some are difficult to overcome separately as the material of positive active material, and are on the low side such as specific capacity, price is higher, cycle performance is not very good and the potential safety hazard factor is relatively outstanding etc.Polyanion type compound has good performance as cathode active material for lithium secondary battery, very likely is pushed to be third generation cathode active material for lithium secondary battery.
Polyanion type compound is a series of tetrahedron or octahedra anion structure unit (XO of containing
m)
N-The general name of the compound of (X=P, S, As, Mo and W).These construction units are linked to be three-dimensional net structure by strong covalent bond and form the space that is occupied by other metal ion of higher coordination, so that polyanion type compound-material has the crystal phase structure different with the metallic compound material and by the various outstanding performance of structures shape.What report was many at present is the polyanion shaped material with olivine and two kinds of structure types of NASICON.This series material has two outstanding advantages: the first, and the crystal frame structure of material is stable, even if a large amount of lithium secondary takes off embedding, this point and the metal oxide of the second generation have larger different; The second, be easy to the discharge potential platform of modulation material.But the shortcoming of polyanion shaped material is that conductance is lower, and the heavy-current discharge performance of material is relatively poor.Mostly be material to be carried out the methods such as carbon coating or doping high-valency metal to improve its electronic conductivity to the method for material modification at present, but it is not ideal to improve effect.
For this reason, disclose a kind of positive active material among the US 2007/0207385A1, comprised compound one and compound two, compound one general formula A
3xM1
2y(PO
4)
3Represent that compound two is for being selected from SiC, BN and formula M 2
aO
bAt least a compound in the group that the metal oxide of expression forms and be coated on the surface of compound one, wherein, A is for being selected from least a atom among IA, IIA, the IIIA, M1 and M2 respectively do for oneself and are selected from least a element in the group that is comprised of IIA, IIIA, IVA and VA and transition metal, are preferably separately at least a element in the group that is comprised of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Be, Mg, Ca, Sr, B, Al, Sn, Ga, In, Si and Ge.And enumerated in an embodiment LiFePO
4/ ZnO/C, LiFePO
4/ ZnAlO
2/ C, LiFePO
4/ CuO/C and LiFePO
4/ ZnAlO/C.
Although above-mentionedly increase by the electronic conductivity that coats the positive active material that compound two obtains on the surface of compound one, its electronic conductivity is still lower, generally only is 10
-5S/cm, and the specific discharge capacity of the battery that is made by this positive active material is lower, cycle performance is relatively poor.
Summary of the invention
The defective that specific discharge capacity is lower, cycle performance is relatively poor of the battery that the electronic conductivity that the object of the invention is to overcome existing positive active material is lower, made by this positive active material, thus provide specific discharge capacity that a kind of electronic conductivity of the positive active material that can Effective Raise makes can improve battery and cycle performance positive active material preparation method and the positive active material that is made by this preparation method and comprise the anodal of this positive active material and comprise the battery that this is anodal.
The invention provides a kind of preparation method of positive active material, wherein, this preparation method comprises that with a kind of mixture sintering this mixture contains raw material one and raw material two, and described raw material one is general formula Li
xM '
y(XO
4)
z, LiM ' XO
5, LiM ' XO
6, LiM ' X
2O
7In the compound of expression one or more, 0＜x/z≤1,0＜y/z≤1.1, M ' is one or more among Na, Mn, Fe, Co, Ni, Ti, V, Y, Mg, Ca, the Zn, X is P, S, As, Mo or W; Described raw material two is general formula A
aM
bN
cO
dIn the compound of expression one or more, A, M, N are different in twos, respectively do for oneself IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII family metallic element, 0≤a≤6,0≤b≤6,0＜c≤6,0＜d≤12, and a, b are not 0 simultaneously.
The present invention also provides a kind of positive active material that is made by above-mentioned preparation method.
The present invention also provides a kind of positive pole, this positive pole comprises plus plate current-collecting body and coating and/or is filled in positive electrode on this plus plate current-collecting body, described positive electrode contains positive active material and adhesive, and wherein, described positive active material is positive active material provided by the invention.
The present invention also provides a kind of lithium secondary battery, this lithium secondary battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, wherein, described positive pole just very provided by the invention.
Data from table 1 of the present invention can find out that the electronic conductivity of the positive active material that method provided by the invention makes can reach 1.8S/cm; Forming in the identical situation, Comparative Examples 1 is passed through ZnAlO
2Be coated on LiFePO with C
4The surface and the electronic conductivity of the positive active material that obtains only is 2.6 * 10
-5S/cm, the electronic conductivity of the positive active material that makes by the embodiment of the invention 7 then are 0.5S/cm, the latter be the former more than 19000 doubly.
In addition, data from table 2 of the present invention can be found out, the initial discharge specific discharge capacity of the battery A1-A15 that the positive active material that is made by method provided by the invention is made all is significantly higher than the reference cell AC1 of Comparative Examples, in the identical situation of other condition, the specific discharge capacity of the battery A7 that the positive active material that is made by method provided by the invention is made is 126 MAh/gs, and reference cell AC1 then only is 112 MAh/gs; Capacity dimension holdup after the battery A7 circulation 500 times is 96.44%, and reference cell AC1 only is 90.12% at the capacity dimension holdup of circulation after 500 times, has illustrated that thus positive electrode active material mass-energy that method provided by the invention makes significantly improves specific discharge capacity and the cycle performance of battery.
Description of drawings
Fig. 1 is the XRD diffraction pattern of the positive active material of embodiment 1 preparation;
Fig. 2 is the XRD diffraction pattern of the positive active material of embodiment 2 preparations;
Fig. 3 is the XRD diffraction pattern of the positive active material of embodiment 3 preparations;
Fig. 4 is the XRD diffraction pattern of the positive active material of embodiment 4 preparations;
Fig. 5 is the XRD diffraction pattern of the positive active material of embodiment 5 preparations;
Fig. 6 is the XRD diffraction pattern of the positive active material of embodiment 6 preparations.
Embodiment
The invention provides a kind of preparation method of positive active material, wherein, this preparation method comprises that with a kind of mixture sintering this mixture contains raw material one and raw material two, and described raw material one is general formula Li
xM '
y(XO
4)
z, LiM ' XO
5, LiM ' XO
6, LiM ' X
2O
7In the compound of expression one or more, 0＜x/z≤1,0＜y/z≤1.1, M ' is one or more among Na, Mn, Fe, Co, Ni, Ti, V, Y, Mg, Ca, the Zn, X is P, S, As, Mo or W; Described raw material two is general formula A
aM
bN
cO
dIn the compound of expression one or more, A, M, N are different in twos, respectively do for oneself IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII family metallic element, 0≤a≤6,0≤b≤6,0＜c≤6,0＜d≤12, and a, b are not 0 simultaneously.
Product behind raw material one of the present invention and raw material two sintering is mixed crystal, described mixed crystal refers to the mixed crystal that two or more compound forms through oversintering, chemical reaction does not occur between this two or more the compound, but the electronic conductivity with obvious raising, its mechanism may be interpreted as: between this two or more the compound chemical reaction does not occur, but in the process of sintering, but introduced a large amount of crystal defects, changed the electronics bonding state between the compound, so that mixed crystal a large amount of oxygen rooms and/or metal gap atom occur owing to lacking oxygen atom.These oxygen rooms and/or metal gap atom provide charge carrier, so that the electronic conductivity of this mixed crystal is greatly improved.
The electronic conductivity of the positive active material that method provided by the invention makes under 25 ℃ can reach 0.01-10S/cm, is preferably 0.1-2S/cm.
Wherein, the mol ratio of described raw material one and raw material two can be 1: 0.01-0.05.
Described raw material two can make with method as described below: with the oxygenatedchemicals of the oxygenatedchemicals of the oxygenatedchemicals of A, M and N with the ratio of mol ratio A: M: N=a: b: c at 400-1000 ℃ of lower sintering 8-15 hour.The sintering afterproduct can adopt the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company to measure, and obtains the XRD diffraction pattern, compare with standard diagram, thus the chemical formula of the product that affirmation makes.Wherein, the oxygenatedchemicals of described A can be for generating the compound of the oxide of A behind the oxide of A and/or the sintering, the compound that can generate the oxide of A behind the described sintering can be in the bicarbonate of the carbonate of the hydroxide of A, A, A one or more.The oxygenatedchemicals of described M can be for generating the compound of the oxide of M behind the oxide of M and/or the sintering, the compound that can generate the oxide of M behind the described sintering can be in the bicarbonate of the carbonate of the hydroxide of M, M, M one or more.The oxygenatedchemicals of described N can be for generating the compound of the oxide of N behind the oxide of N and/or the sintering, the compound that can generate the oxide of N behind the described sintering can be in the bicarbonate of the carbonate of the hydroxide of N, N, N one or more.
Among the present invention, general formula Li
xM '
y(XO
4)
zRepresented described raw material one can be olivine-type, NASICON type or monoclinic form, and the example of olivine-type can be enumerated LiMnPO
4, LiCoPO
4Deng, the example of NASICON type or monoclinic form can be enumerated Li
3Fe
2(PO
4)
3, LiTi
2(PO
4)
3, Li
3V
2(PO
4)
3, Li
2NaV
2(PO
4)
3Deng, general formula LiM ' XO
5Represented described raw material one can be enumerated LiTiPO
5, general formula LiM ' XO
6Represented described raw material one can be enumerated LiVMoO
6, LiVWO
6Deng, general formula LiM ' X
2O
7Represented described raw material one can be enumerated LiVP
2O
7, LiFeAs
2O
7Deng.
Wherein, general formula Li
XxM '
Yy(XO
4)
ZzIn the represented described raw material one, M ' is preferably one or more among Fe or Fe and Mn, Co, Ni, Ti, Y, Mg, Ca, the Zn, and the shared molar ratio of Fe is 90-100% among the M '.Specifically can list LiFePO
4, Li
0.99Y
0.01FePO
4And LiR
iFe
1-iPO
4In the compound of expression one or more, wherein, 0＜i≤0.1, R is one or more among Co, Mn, Mg, Ca, Ni, Zn, the Ti.
Described raw material two can be Bi
4Ti
3O
12, CuNb
2O
6, MnTaO
4, FeWO
4, ZnZrNb
2O
8, NiNb
2O
6, NiZrNb
2O
8, FeTiNb
2O
8, MnTiNb
2O
8, MgSnNb
2O
8, ZnTa
2O
6, Cu
0.85Zn
0.15Nb
2O
6, YBa
3Ti
2O
8.5, Zr
0.75Ti
0.75Sn
0.5O
4, HfTiO
4, MgNb
2O
6In one or more.
Under the preferable case, described mixture can also contain carbon source, the consumption of described carbon source so that in the positive active material of gained the content of carbon be the 1-5 % by weight.According to this preferred implementation, can further improve the electronic conductivity of prepared positive active material.Described carbon source can be various carbon sources well known in the art, for example can be DIC source and/or organic carbon source, described inorganic carbon source can be in carbon black, acetylene black, the graphite one or more, and described organic carbon source can be in glucose, sucrose, citric acid, starch, dextrin, the polyethylene glycol one or more.
The condition of described sintering can comprise that the heating rate with 5-20 ℃/min is warming up to 500-850 ℃, in 500-850 ℃ of lower sintering 5-32 hour; The atmosphere of described sintering is different because of the difference of raw material, and easy when oxidized under described sintering temperature when raw material, the atmosphere of described sintering is preferably inert atmosphere or reducing atmosphere; When raw material is difficult under described sintering temperature when oxidized, the atmosphere of described sintering can be any atmosphere.
The present invention also provides a kind of positive active material, and wherein, this positive active material is made by above-mentioned preparation method.
Need to prove, described in background technology of the present invention, although disclosed positive active material also comprises compound one and compound two among the US 2007/0207385A1, compound one general formula A
3xM1
2y(PO
4)
3Represent that compound two is for being selected from SiC, BN and formula M 2
aO
bAt least a compound in the group that the metal oxide of expression forms and be coated on the surface of compound one, wherein, A is for being selected from least a atom among IA, IIA, the IIIA, M1 and M2 respectively do for oneself and are selected from least a element in the group that is comprised of IIA, IIIA, IVA and VA and transition metal, and have specifically enumerated positive active material LiFePO in embodiment
4/ ZnO/C, LiFePO
4/ ZnAlO
2/ C, LiFePO
4/ CuO/C and LiFePO
4/ ZnAlO/C, but in US 2007/0207385A1, be to prepare as follows positive active material:
(S11) preparation contains A ion, M1 ion and PO
4 3-The solution of ion,
(S12) add M2 salt in mentioned solution,
(S13) pH that regulates mentioned solution is with formation M2 hydroxide, and so that M2 hydroxide becomes the M2 oxide.
(S14) make the dry and sintering of solution of the above-mentioned M2 of containing oxide, be coated with M2 to form the surface
aO
bA
3xM1
2y(PO
4)
3
Can find out that from above-mentioned preparation method although sintering is also arranged among the US 2007/0207385A1, this sintering is in order to obtain end product ... the surface is coated with M2
aO
bA
3xM1
2y(PO
4)
3, and only pass through M2
aO
bCoat A
3xM1
2y(PO
4)
3The surface and the positive active material that obtains can not reach of the present invention and is the 0.01-10S/cm high electronic conductivities of 0.1-2S/cm particularly down at 25 ℃, and the product of the present invention after with raw material one and raw material two sintering is mixed crystal, this mixed crystal is the anoxic attitude, contain aerobic room and/or metal gap atom, the effect that these oxygen rooms and/or metal gap atom can play donor level improves the electronic conductivity of this mixed crystal, thereby can improve the electronic conductivity of the positive active material that the present invention makes, therefore the positive active material that makes of method provided by the invention is different from the positive active material described in the US 2007/0207385A1.
In addition, the present invention also provides a kind of positive pole, and this positive pole comprises plus plate current-collecting body and coating and/or be filled in positive electrode on this plus plate current-collecting body that described positive electrode contains positive active material and adhesive, wherein, described positive active material is positive active material provided by the invention.
Described adhesive can adopt any adhesive known in those skilled in the art, and preferred described adhesive is the mixture of hydrophobicity adhesive and hydrophilic adhesive.The ratio of described hydrophobicity adhesive and hydrophilic adhesive has no particular limits, and can determine according to actual needs, and for example, the part by weight of hydrophilic adhesive and hydrophobicity adhesive can be 0.3: 1-1: 1.Described adhesive can use with the aqueous solution or emulsion form, also can use with solid form, preferably use with the aqueous solution or emulsion form, have no particular limits the concentration of described hydrophilic adhesive solution and the concentration of described hydrophobicity adhesive agent emulsion this moment, the viscosity that can be coated with according to the slurry of positive pole to be prepared and cathode size and the requirement of operability are adjusted flexibly to this concentration, for example the concentration of described hydrophilic adhesive solution can be the 0.5-4 % by weight, and the concentration of described hydrophobicity adhesive agent emulsion can be the 10-80 % by weight.Described hydrophobicity adhesive can be polytetrafluoroethylene, butadiene-styrene rubber or their mixture.Described hydrophilic adhesive can be hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol or their mixture.The content of described adhesive is the 0.01-8 % by weight of positive active material, is preferably the 1-5 % by weight.
Under the preferable case, described positive electrode can also contain conductive agent, and described conductive agent can adopt any conductive agent known in those skilled in the art, for example can adopt in graphite, carbon fiber, carbon black, metal dust and the fiber one or more.The content of described conductive agent can for, for example, the 0.1-20 % by weight of described positive electrode total weight is preferably the 2-10 % by weight.
Described plus plate current-collecting body can be aluminium foil, Copper Foil, nickel plated steel strip or Punching steel strip.
The preparation method of described positive pole can adopt this area the whole bag of tricks commonly used, for example with solvent positive active material, adhesive and conductive agent are prepared into anode sizing agent, then prepared anode sizing agent slurry is coated in dry compressing tablet on the positive electrode collector, cut-parts obtain positive pole again.The temperature of described drying can be 100-150 ℃, and can be 2-10 hour drying time.
The used solvent of described anode sizing agent can be the various solvents that use in the prior art, as being selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The addition of this solvent is conventionally known to one of skill in the art, and the viscosity that can be coated with according to the slurry of anode sizing agent to be prepared and the requirement of operability are adjusted flexibly, described anode sizing agent can be coated on the described plus plate current-collecting body get final product.In general, it is the 40-90 % by weight that the consumption of this solvent makes the content of positive active material in the anode sizing agent, is preferably the 50-85 % by weight.
The present invention also provides a kind of lithium secondary battery, this lithium secondary battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, wherein, described positive pole just very provided by the invention.
In lithium secondary battery, barrier film is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.In the present invention, described barrier film can be selected from and well known to a person skilled in the art various barrier films used in the lithium secondary battery, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
Described negative pole can adopt negative pole known in the field, and in general, negative pole comprises negative current collector and coating and/or is filled in negative material on this negative current collector.Described conductive current collector is conventionally known to one of skill in the art, for example can be in aluminium foil, Copper Foil, nickel plated steel strip, the Punching steel strip a kind of.Anticathode material of the present invention has no particular limits, and is the same with prior art, and described negative material contains negative electrode active material and adhesive usually.Described negative electrode active material can adopt various negative electrode active materials commonly used in the prior art, for example material with carbon element.Described material with carbon element can be non-graphitic carbon, graphite or the charcoal that obtained by high-temperature oxydation by polyyne family macromolecule material, also can use other material with carbon element such as pyrolytic carbon, coke, organic polymer sinter, active carbon etc.Described organic polymer sinter can be by the product with gained after the sintering such as phenolic resins, epoxy resin and the charing.
Described adhesive can be selected from the adhesive of lithium secondary battery routine, such as in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC) and the butadiene-styrene rubber (SBR) one or more.In general, the content of described adhesive is the 0.5-8 % by weight of negative electrode active material, is preferably the 2-5 % by weight.
Under the preferable case, described negative material can also contain conductive agent.Because conductive agent for increasing the conductivity of electrode, reduce the internal resistance of battery, so the present invention preferably contains conductive agent.The content of described conductive agent and kind are conventionally known to one of skill in the art, and for example, take negative material as benchmark, the content of conductive agent is generally the 0.1-12 % by weight.Described conductive agent can be selected from one or more in conductive carbon black, nickel powder, the copper powder.
The preparation method of described negative pole can adopt this area the whole bag of tricks commonly used, for example with solvent the conductive agent that negative electrode active material, adhesive and selectivity contain is prepared into cathode size, then prepared cathode size slurry is coated in dry compressing tablet on the negative electrode collector, cut-parts obtain negative pole again.The temperature of described drying can be 100-150 ℃, and can be 2-10 hour drying time.
The used solvent of described cathode size can be the various solvents that use in the prior art, as being selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The addition of this solvent is conventionally known to one of skill in the art, and the viscosity that can be coated with according to the slurry of cathode size to be prepared and the requirement of operability are adjusted flexibly, described cathode size can be coated on the described negative current collector get final product.In general, it is the 40-90 % by weight that the consumption of this solvent makes the content of negative electrode active material in the cathode size, is preferably the 50-85 % by weight.
In lithium secondary battery of the present invention, described electrolyte can be nonaqueous electrolytic solution.The solution that described nonaqueous electrolytic solution can form in nonaqueous solvents for electrolyte lithium salt.In the present invention, can use and well known to a person skilled in the art various nonaqueous electrolytic solutions.For example, described electrolyte lithium salt can be selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based Sulfonic Lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more; Described nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more.In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt can be the 0.1-2 mol/L, is preferably the 0.8-1.2 mol/L.
The preparation method of lithium secondary battery provided by the invention can be method as well known to those skilled in the art, in general, this preparation method comprises and positive pole, barrier film and negative pole being reeled successively or stacked to form electrode cores, this electrode cores is inserted in the battery case, add electrolyte, then sealing obtains lithium secondary battery.Wherein, described coiling or method overlapping and sealing can be the known methods of those skilled in the art.The consumption of described electrolyte can adopt conventional amount used known in those skilled in the art.
The present invention is described in detail below by embodiment.
With MnCO
3, TiO
2, Nb
2O
5Mix as 1: 1: 1 ratio take mol ratio, ball milling 5 hours is warming up to 500 ℃ of roastings 10 hours with 10 ℃/min under nitrogen atmosphere, obtain sintered product.The XRD diffraction pattern of this sintered product that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is with MnTiNb
2O
8Standard diagram is compared, thereby confirms that this sintered product is MnTiNb
2O
8
With LiFePO
4With the above-mentioned MnTiNb that makes
2O
8Mixing according to 1: 0.04 ratio of mol ratio, is that the amount of 5 % by weight adds the starch as carbon source according to the content of carbon in the positive active material that generates then, and ball milling 10 hours mixes; Then the mixture that ball milling is good is warming up to 600 ℃ with dried powder heating rate with 10 ℃/min under argon gas atmosphere 80 ℃ of oven dry, carries out the constant temperature sintering 20 hours, obtains positive active material LiFePO
4/ MnTiNb
2O
8The mixed crystal of/C.
Adopt the XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 1, in the diffraction maximum of the positive active material that as can be seen from Figure 1 behind above-mentioned sintering, makes, except LiFePO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiFePO
4/ MnTiNb
2O
8The mixed crystal of/C.
Embodiment 2
With ZnO, Ta
2O
5Mix as 1: 1 ratio take mol ratio, ball milling 5 hours is warming up to 800 ℃ of roastings 8 hours with 15 ℃/min under air atmosphere, obtain sintered product.The XRD diffraction pattern of this sintered product that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is with ZnTa
2O
6Standard diagram is compared, thereby confirms that this sintered product is ZnTa
2O
6
With LiFePO
4With the above-mentioned ZnTa that makes
2O
6Mix according to 1: 0.03 ratio of mol ratio, ball milling 10 hours mixes; Then the mixture that ball milling is good is warming up to 500 ℃ with dried powder heating rate with 5 ℃/min under argon gas atmosphere 80 ℃ of oven dry, carries out the constant temperature sintering 30 hours, obtains positive active material LiFePO
4/ ZnTa
2O
6Mixed crystal.
Adopt the XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 2, in the diffraction maximum of the positive active material that as can be seen from Figure 2 behind above-mentioned sintering, makes, except LiFePO
4And ZnTa
2O
6Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And ZnTa
2O
6Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiFePO
4/ ZnTa
2O
6Mixed crystal.
Embodiment 3
With Y
2O
3, BaCO
3, TiO
2Mix as 0.5: 3: 2 ratio take mol ratio, ball milling 5 hours is warming up to 1000 ℃ of roastings 15 hours with 7 ℃/min under nitrogen atmosphere, obtain sintered product.The XRD diffraction pattern of this sintered product that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is with YBa
3Ti
3O
8.5Standard diagram is compared, thereby confirms that this sintered product is YBa
3Ti
2O
8.5
With LiFePO
4With the above-mentioned YBa that makes
3Ti
2O
8.5Mixing according to 1: 0.02 ratio of mol ratio, is that the amount of 2 % by weight adds the carbon black as carbon source according to the content of carbon in the positive active material that generates then, and ball milling 10 hours mixes; Then the mixture that ball milling is good is warming up to 800 ℃ with dried powder heating rate with 20 ℃/min under argon gas atmosphere 80 ℃ of oven dry, carries out the constant temperature sintering 8 hours, obtains positive active material LiFePO of the present invention
4/ YBa
3Ti
2O
8.5The mixed crystal of/C.
Adopt the XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 3, in the diffraction maximum of the positive active material that as can be seen from Figure 3 behind above-mentioned sintering, makes, except LiFePO
4And YBa
3Ti
2O
8.5Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And YBa
3Ti
2O
8.5Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiFePO
4/ YBa
3Ti
2O
8.5The mixed crystal of/C.
With CuO, ZnO, Nb
2O
5Mix as 0.85: 0.15: 1 ratio take mol ratio, ball milling 5 hours is warming up to 1000 ℃ of roastings 15 hours with 7 ℃/min under nitrogen atmosphere, obtain sintered product.The XRD diffraction pattern of this sintered product that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is with Cu
0.85Zn
0.15Nb
2O
6Standard diagram is compared, thereby confirms that this sintered product is Cu
0.85Zn
0.15Nb
2O
6
Prepare positive active material according to embodiment 1 described method, different is to use respectively LiCoPO
4Replace LiFePO
4, with the above-mentioned Cu that makes
0.85Zn
0.15Nb
2O
6Replace MnTiNb
2O
8, make positive active material LiCoPO
4/ Cu
0.85Zn
0.15Nb
2O
6The mixed crystal of/C.
Adopt the XRD diffraction pattern of this positive electrode that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 4, in the diffraction maximum of the positive active material that as can be seen from Figure 4 behind above-mentioned sintering, makes, except LiCoPO
4And Cu
0.85Zn
0.15Nb
2O
6Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiCoPO in this positive active material be described
4And Cu
0.85Zn
0.15Nb
2O
6Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiCoPO
4/ Cu
0.85Zn
0.15Nb
2O
6The mixed crystal of/C.
Embodiment 5
With ZrO
2, TiO
2, SnO
2Mix as 0.75: 0.75: 0.5 ratio take mol ratio, ball milling 5 hours is warming up to 1000 ℃ of roastings 15 hours with 7 ℃/min under nitrogen atmosphere, obtain sintered product.The XRD diffraction pattern of this sintered product that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is with Zr
0.75Ti
0.75Sn
0.5O
4Standard diagram is compared, thereby confirms that this sintered product is Zr
0.75Ti
0.75Sn
0.5O
4
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned Zr that makes
0.75Ti
0.75Sn
0.5O
4Replace MnTiNb
2O
8, make positive active material LiFePO
4/ Zr
0.75Ti
0.75Sn
0.5O
4The mixed crystal of/C.
Adopt the XRD diffraction pattern of this positive electrode that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 5, in the diffraction maximum of the positive active material that as can be seen from Figure 5 behind above-mentioned sintering, makes, except LiFePO
4And Zr
0.75Ti
0.75Sn
0.5O
4Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And Zr
0.75Ti
0.75Sn
0.5O
4Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiFePO
4/ Zr
0.75Ti
0.75Sn
0.5O
4The mixed crystal of/C.
Embodiment 6
With FeO, WO
3Mix as 1: 1 ratio take mol ratio, ball milling 5 hours is warming up to 800 ℃ of roastings 8 hours with 15 ℃/min under air atmosphere, obtain sintered product.The XRD diffraction pattern of this sintered product that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is with FeWO
4Standard diagram is compared, thereby confirms that this sintered product is FeWO
4
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned FeWO that makes
4Replace MnTiNb
2O
8, make positive active material LiFePO
4/ FeWO
4The mixed crystal of/C.
Adopt the XRD diffraction pattern of this positive electrode that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 6, in the diffraction maximum of the positive active material that as can be seen from Figure 6 behind above-mentioned sintering, makes, except LiFePO
4And FeWO
4Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And FeWO
4Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiFePO
4/ FeWO
4The mixed crystal of/C.
Embodiment 7
With ZnO, Al
2O
3Mix as 2: 1 ratio take mol ratio, ball milling 5 hours is warming up to 800 ℃ of roastings 8 hours with 15 ℃/min under air atmosphere, obtain sintered product.The XRD diffraction pattern of this sintered product that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is with ZnAlO
2Standard diagram is compared, thereby confirms that this sintered product is ZnAlO
2
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned ZnAlO that makes
2Replace MnTiNb
2O
8, make positive active material LiFePO
4/ ZnAlO
2The mixed crystal of/C.
The XRD diffraction pattern of this positive electrode that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiFePO
4And ZnAlO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And ZnAlO
2Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiFePO
4/ ZnAlO
2The mixed crystal of/C.
Comparative Examples 1
Prepare positive active material LiFePO according to the disclosed method of Example B among the US 2007/0207385A1
4And ZnAlO
2Mol ratio be 1: 0.04, the content of carbon be 5 % by weight by ZnAlO
2Be coated on LiFePO with C
4The surface and the positive active material LiFePO that forms
4/ ZnAlO
2/ C.
Embodiment 8
" anode material for lithium-ion batteries Li in " functional material " the 5th phase in 2005 of employing (36) volume
0.99Y
0.01FePO
4Preparation " method described in the literary composition prepares Li
0.99Y
0.01FePO
4
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned Li that makes
0.99Y
0.01FePO
4Replace LiFePO
4, make positive active material Li
0.99Y
0.01FePO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except Li
0.99Y
0.01FePO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained Li in this positive active material be described
0.99Y
0.01FePO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is Li
0.99Y
0.01FePO
4/ MnTiNb
2O
8The mixed crystal of/C.
Embodiment 9
Adopt interim " the anode material for lithium-ion batteries LiNi of volume the 4th in " China YouSe Acta Metallurgica Sinica " April in 2006 the 16th
0.1Fe
0.9PO
4Synthetic and performance " method described in the literary composition, with Li
2CO
3, FeC
2O
42H
2O, NH
4H
2PO
4And TiO
2With LiTi
0.05Fe
0.95PO
4Stoichiometric proportion mix, ball milling is 5 hours in ethanol medium, the gained powder dries to remove ethanol at low temperatures, then with mixed-powder under the protection of argon gas, be warming up to 320 ℃ of constant temperature 7 hours, 700 ℃ of lower sintering 24 hours, make LiTi again
0.05Fe
0.95PO
4
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiTi that makes
0.05Fe
0.95PO
4Replace LiFePO
4, make positive active material LiTi
0.05Fe
0.95PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiTi
0.05Fe
0.95PO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiTi in this positive active material be described
0.05Fe
0.95PO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiTi
0.05Fe
0.95PO
4/ MnTiNb
2O
8The mixed crystal of/C.
Adopt interim " the anode material for lithium-ion batteries LiNi of volume the 4th in " China YouSe Acta Metallurgica Sinica " April in 2006 the 16th
0.1Fe
0.9PO
4Synthetic and performance " method described in the literary composition, with Li
2CO
3, FeC
2O
42H
2O, NH
4H
2PO
4And Ni (CH
3COO)
24H
2O is with LiNi
0.1Fe
0.9PO
4Stoichiometric proportion mix, ball milling is 5 hours in ethanol medium, the gained powder dries to remove ethanol at low temperatures, then with mixed-powder under the protection of argon gas, be warming up to 320 ℃ of constant temperature 7 hours, 700 ℃ of lower sintering 24 hours, make LiNi again
0.1Fe
0.9PO
4
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiNi that makes
0.1Fe
0.9PO
4Replace LiFePO
4, make positive active material LiNi
0.1Fe
0.9PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiNi
0.1Fe
0.9PO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiNi in this positive active material be described
0.1Fe
0.9PO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiNi
0.1Fe
0.9PO
4/ MnTiNb
2O
8The mixed crystal of/C.
Embodiment 11
Adopt embodiment 10 described methods to prepare LiCo
0.01Fe
0.99PO
4, different is to replace Ni (CH with CoO
3COO)
24H
2O and with LiCo
0.01Fe
0.99PO
4Stoichiometric proportion mix.
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiCo that makes
0.01Fe
0.99PO
4Replace LiFePO
4, make positive active material LiCo
0.01Fe
0.99PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiCo
0.01Fe
0.99PO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiCo in this positive active material be described
0.01Fe
0.99PO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiCo
0.01Fe
0.99PO
4/ MnTiNb
2O
8The mixed crystal of/C.
Embodiment 12
Adopt embodiment 10 described methods to prepare LiMn
0.02Fe
0.98PO
4, different is to use MnCO
3Replace Ni (CH
3COO)
24H
2O and with LiMn
0.02Fe
0.98PO
4Stoichiometric proportion mix.
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiMn that makes
0.02Fe
0.98PO
4Replace LiFePO
4, make positive active material LiMn
0.02Fe
0.98PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiMn
0.02Fe
0.98PO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiMn in this positive active material be described
0.02Fe
0.98PO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiMn
0.02Fe
0.98PO
4/ MnTiNb
2O
8The mixed crystal of/C.
Embodiment 13
Adopt embodiment 10 described methods to prepare LiMg
0.03Fe
0.97PO
4, different is to replace Ni (CH with MgO
3COO)
24H
2O and with LiMg
0.03Fe
0.97PO
4Stoichiometric proportion mix.
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiMg that makes
0.03Fe
0.97PO
4Replace LiFePO
4, make positive active material LiMg
0.03Fe
0.97PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiMg
0.03Fe
0.97PO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiMg in this positive active material be described
0.03Fe
0.97PO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiMg
0.03Fe
0.97PO
4/ MnTiNb
2O
8The mixed crystal of/C.
Embodiment 14
Adopt embodiment 10 described methods to prepare LiCa
0.05Fe
0.95PO
4, different is to replace Ni (CH with CaO
3COO)
24H
2O and with LiCa
0.05Fe
0.95PO
4Stoichiometric proportion mix.
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiCa that makes
0.05Fe
0.95PO
4Replace LiFePO
4, make positive active material LiCa
0.05Fe
0.95PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiCa
0.05Fe
0.95PO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiCa in this positive active material be described
0.05Fe
0.95PO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiCa
0.05Fe
0.95PO
4/ MnTiNb
2O
8The mixed crystal of/C.
Embodiment 15
Adopt embodiment 10 described methods to prepare LiZn
0.07Fe
0.93PO
4, different is to use ZnCO
3Replace Ni (CH
3COO)
24H
2O and with LiZn
0.07Fe
0.93PO
4Stoichiometric proportion mix.
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiZn that makes
0.07Fe
0.93PO
4Replace LiFePO
4, make positive active material LiZn
0.07Fe
0.93PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The XRD diffraction pattern of this positive active material that the D/MAX-2200/PC type x-ray powder diffraction instrument of employing Rigaku company records is in the diffraction maximum of the positive active material that makes behind above-mentioned sintering as can be seen from the figure, except LiZn
0.07Fe
0.93PO
4And MnTiNb
2O
8Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiZn in this positive active material be described
0.07Fe
0.93PO
4And MnTiNb
2O
8Still exist with two phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiZn
0.07Fe
0.93PO
4/ MnTiNb
2O
8The mixed crystal of/C.
The electronic conductivity test of positive active material
The positive active material that under 25 ℃ embodiment 1-15 and Comparative Examples 1 is made respectively depresses to cylinder in the briquetting pressure of 30MPa, then measure respectively this cylindrical height l, bottom surface diameter d and resistance R, calculate respectively the electronic conductivity σ of embodiment 1-15 and Comparative Examples 1 positive active material, σ=4l/ (π Rd by following formula
2), the result is as shown in table 1 below.
Table 1
| The positive active material source | Electronic conductivity (S/cm) under 25 ℃ of positive |
| Embodiment | |
| 1 | 0.175 |
| Embodiment 2 | 0.21 |
| Embodiment 3 | 1.8 |
| |
1.2 |
| Embodiment 5 | 1.5 |
| Embodiment 6 | 0.8 |
| Embodiment 7 | 0.5 |
| Comparative Examples 1 | 2.6×10 -5 |
| Embodiment 8 | 0.83 |
| Embodiment 9 | 0.76 |
| |
0.63 |
| Embodiment 11 | 0.94 |
| Embodiment 12 | 0.87 |
| Embodiment 13 | 1.3 |
| Embodiment 14 | 0.96 |
| Embodiment 15 | 0.83 |
Embodiment 16-30 and Comparative Examples 2
(1) anodal preparation
The positive active material and 5 that respectively 90 grams is made by embodiment 1-15 and Comparative Examples 1 restrains adhesive Kynoar (PVDF) and 5 gram conductive agent acetylene blacks join in the 50 gram 1-METHYLPYRROLIDONEs, then stirs in de-airing mixer and forms uniform anode sizing agent.This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, then in 150 ℃ of lower oven dry, roll-in, cut to make and be of a size of 540 * 43.5 millimeters positive pole, wherein contain the positive active materials of 5.2 grams of having an appointment.
(2) preparation of battery
The preparation of negative pole
90 gram negative electrode active material native graphites, 5 gram adhesive Kynoar, 5 gram conductive agent carbon blacks are joined in the 100 gram 1-METHYLPYRROLIDONEs, then in de-airing mixer, stir and form uniform cathode size.This cathode size is coated on the both sides that thickness is 12 microns Copper Foil equably, then in 90 ℃ of lower oven dry, roll-in, cut to make and be of a size of 500 * 44 millimeters negative pole, wherein contain the 3.8 gram negative electrode active material native graphites of having an appointment.
The assembling of battery
Respectively above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium secondary battery, subsequently with LiPF
6Concentration by 1 mol/L is dissolved in EC/EMC/DEC=1: form nonaqueous electrolytic solution in 1: 1 the mixed solvent, this electrolyte is injected battery aluminum shell with the amount of 3.8g/Ah, lithium secondary secondary cell A1-A15, AC1 are made respectively in sealing.
The performance test of battery
The above-mentioned lithium secondary battery A1-A15 that makes and AC1 are placed on respectively test cashier's office in a shop, under 25 ℃ of conditions, carry out constant current charge with 0.5C first, charging upper limit is 3.8 volts; After shelving 20 minutes, be discharged to 2.5 volts with the electric current of 0.5C from 3.8 volts, the gained capacity is designated as the first discharge capacity of battery, and calculates according to the following equation the specific discharge capacity of battery; The result is as shown in table 2 below.
Specific discharge capacity=battery is discharge capacity (MAH)/positive active material weight (gram) first
Then repeat above-mentioned charging, shelve, after the discharge step each 500 times, the discharge capacity of record battery.By the capacity dimension holdup after the following formula computation cycles 500 times.The capacity dimension holdup is larger, illustrates that then the cycle performance of battery is better.The result is as shown in table 2 below.
Capacity dimension holdup=(the N time cyclic discharge capacity/first discharge capacity) * 100%
Table 2
| The battery source | The battery numbering | Specific discharge capacity (MAh/g, 0.5C) | Capacity dimension holdup after 500 times circulates |
| Embodiment 16 | A1 | 123 | 95.21％ |
| Embodiment 17 | A2 | 124 | 95.87％ |
| Embodiment 18 | A3 | 135 | 98.87％ |
| Embodiment 19 | A4 | 131 | 97.56 |
| Embodiment | |||
| 20 | A5 | 133 | 98.50％ |
| Embodiment 21 | A6 | 128 | 97.05％ |
| Embodiment 22 | A7 | 126 | 96.44％ |
| Comparative Examples 2 | AC1 | 112 | 90.12％ |
| Embodiment 23 | A8 | 128 | 97.10％ |
| Embodiment 24 | A9 | 127 | 97.01％ |
| Embodiment 25 | A10 | 126 | 96.87％ |
| Embodiment 26 | A11 | 129 | 97.25％ |
| Embodiment 27 | A12 | 129 | 97.15％ |
| Embodiment 28 | A13 | 132 | 97.87％ |
| Embodiment 29 | A14 | 129 | 97.26％ |
| Embodiment 30 | A15 | 128 | 97.10％ |
Data from above-mentioned table 1 can find out that the electronic conductivity of the positive active material that method provided by the invention makes can reach 1.8S/cm; Forming in the identical situation, Comparative Examples 1 is passed through ZnAlO
2Be coated on LiFePO with C
4The surface and the electronic conductivity of the positive active material that obtains only is 2.6 * 10
-5S/cm, the electronic conductivity of the positive active material that makes by the embodiment of the invention 7 then are 0.5S/cm, the latter be the former more than 19000 doubly.
In addition, data from above-mentioned table 2 can be found out, the initial discharge specific discharge capacity of the battery A1-A15 that the positive active material that is made by method provided by the invention is made all is significantly higher than the reference cell AC1 of Comparative Examples, in the identical situation of other condition, the specific discharge capacity of the battery A7 that the positive active material that is made by method provided by the invention is made is 126 MAh/gs, and reference cell AC1 then only is 112 MAh/gs; Capacity dimension holdup after the battery A7 circulation 500 times is 96.44%, and reference cell AC1 only is 90.12% at the capacity dimension holdup of circulation after 500 times, has illustrated that thus positive electrode active material mass-energy that method provided by the invention makes significantly improves specific discharge capacity and the cycle performance of battery.
Claims (12)
1. the preparation method of a positive active material is characterized in that, this preparation method comprises that with a kind of mixture sintering this mixture contains raw material one and raw material two, and described raw material one is general formula Li
xM '
y(XO
4)
z, LiM ' XO
5, LiM ' XO
6, LiM ' X
2O
7In the compound of expression one or more, 0＜x/z≤1,0＜y/z≤1.1, M ' is one or more among Na, Mn, Fe, Co, Ni, Ti, V, Y, Mg, Ca, the Zn, X is P, S, As, Mo or W; Described raw material two is general formula A
aM
bN
cO
dIn the compound of expression one or more, A, M, N are different in twos, 0≤a≤6,0≤b≤6,0＜c≤6,0＜d≤12, and a, b be not 0 simultaneously, the compound that is represented by above-mentioned general formula is Bi
4Ti
3O
12, CuNb
2O
6, MnTaO
4, ZnZrNb
2O
8, NiNb
2O
6, NiZrNb
2O
8, FeTiNb
2O
8, MnTiNb
2O
8, MgSnNb
2O
8, ZnTa
2O
6, Cu
0.85Zn
0.15Nb
2O
6, YBa
3Ti
2O
8.5, Zr
0.75Ti
0.75Sn
0.5O
4, HfTiO
4, MgNb
2O
6In one or more; Be mixed crystal with the product behind raw material one and raw material two sintering.
2. the preparation method of positive active material according to claim 1, wherein, the mol ratio of described raw material one and raw material two is 1:0.01-0.05.
3. the preparation method of positive active material according to claim 1, wherein, described raw material two is by the oxygenatedchemicals of the oxygenatedchemicals of the oxygenatedchemicals of A, M and the N ratio with mol ratio A:M:N=a:b:c was obtained at 400-1000 ℃ of lower sintering 8-15 hour.
4. the preparation method of positive active material according to claim 1, wherein, M ' is one or more the combination among Fe or Fe and Mn, Co, Ni, Ti, Y, Mg, Ca, the Zn, and the shared molar ratio of Fe is 90-100% among the M '.
5. the preparation method of positive active material according to claim 1, wherein, described raw material one is LiFePO
4, LiMnPO
4, LiCoPO
4, Li
3Fe
2(PO
4)
3, LiTi
2(PO
4)
3, Li
3V
2(PO
4)
3, Li
2NaV
2(PO
4)
3, Li
0.99Y
0.01FePO
4, LiR
iFe
1-iPO
4, LiTiPO
5, LiVMoO
6, LiVWO
6, LiVP
2O
7, LiFeAs
2O
7In one or more, wherein, 0＜i≤0.1, R is one or more among Co, Mn, Mg, Ca, Ni, Zn, the Ti.
6. the preparation method of positive active material according to claim 5, wherein, described raw material one is LiFePO
4, Li
0.99Y
0.01FePO
4And LiR
iFe
1-iPO
4In the compound of expression one or more.
7. the preparation method of the described positive active material of any one according to claim 1-6, wherein, mixture also contains carbon source, the consumption of described carbon source so that in the positive active material of gained the content of carbon be the 1-5 % by weight, described carbon source is one or more in carbon black, graphite, glucose, sucrose, citric acid, starch, dextrin, the polyethylene glycol.
8. the preparation method of positive active material according to claim 7, wherein, described carbon black is acetylene black.
9. the preparation method of positive active material according to claim 1, wherein, the condition of described sintering comprised that the heating rate with 5-20 ℃/min is warming up to 500-850 ℃, in 500-850 ℃ of lower sintering 5-32 hour.
10. a positive active material is characterized in that, this positive active material is made by the described method of any one among the claim 1-9.
11. positive pole, this positive pole comprises plus plate current-collecting body and coating and/or is filled in positive electrode on this plus plate current-collecting body, described positive electrode contains positive active material and adhesive, it is characterized in that, described positive active material is positive active material claimed in claim 10.
12. lithium secondary battery, this lithium secondary battery comprises battery container, electrode group and electrolyte, and electrode group and electrolyte are sealed in the battery container, and the electrode group comprises reels or stacked positive pole, barrier film and negative pole successively, it is characterized in that the described positive pole of described just very claim 11.
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| CN2008101892354A CN101740750B (en) | 2008-11-05 | 2008-12-26 | Method for preparing anode active substance, anode active substance, anode and battery |
| PCT/CN2009/074774 WO2010051749A1 (en) | 2008-11-05 | 2009-11-03 | Method of preparing cathode active material and method of forming lithium secondary battery |
| PCT/CN2009/074769 WO2010051746A1 (en) | 2008-11-05 | 2009-11-03 | Cathode active material, lithium ion secondary battery and rechargable battery having the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810173652 | 2008-11-05 | ||
| CN200810173652.X | 2008-11-05 | ||
| CN2008101892354A CN101740750B (en) | 2008-11-05 | 2008-12-26 | Method for preparing anode active substance, anode active substance, anode and battery |
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| CN101740750B true CN101740750B (en) | 2013-04-10 |
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| CN110148741B (en) * | 2019-06-20 | 2020-09-08 | 山东大学 | Coated lithium niobium molybdate material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2510880A1 (en) * | 2005-07-06 | 2007-01-06 | Michel Gauthier | Process for the preparation of a composite |
| CN1989649A (en) * | 2004-07-26 | 2007-06-27 | 原子能委员会 | Electrode for a lithium battery method for production of such an electrode and lithium battery comprising said electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1989649A (en) * | 2004-07-26 | 2007-06-27 | 原子能委员会 | Electrode for a lithium battery method for production of such an electrode and lithium battery comprising said electrode |
| CA2510880A1 (en) * | 2005-07-06 | 2007-01-06 | Michel Gauthier | Process for the preparation of a composite |
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