CN101740751B - 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
- Publication number
- CN101740751B CN101740751B CN2008101892392A CN200810189239A CN101740751B CN 101740751 B CN101740751 B CN 101740751B CN 2008101892392 A CN2008101892392 A CN 2008101892392A CN 200810189239 A CN200810189239 A CN 200810189239A CN 101740751 B CN101740751 B CN 101740751B
- Authority
- CN
- China
- Prior art keywords
- active material
- positive active
- equal
- raw material
- positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
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: LixxM'yy(XO4)zz, LiM'XO5, LiM'XO6 and LiM'X2O7, wherein xx/zz is more than 0 and less than or equal to 1, yy/zz 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 LiDcO2, LiiNi1-d-eCodMneO2, LiNi1-f-gCofAlgO2, LixNi1-yCoO2 and LimMn2-nEnOj, wherein c is more than 0 and less than or equal to 3, i is more than or equal to 0.9 and less than or equal to 1.2, d is more than or equal to 0 and less than or equal to 0.5, e is more than 0 and less than or equal to 0.3, f is more than or equal to 0 and less than or equal to 0.5, g is more than or equal to 0 and less than or equal to 0.3, x is more than or equal to 0.9 and less than or equal to 1.1, and y is more than or equal to 0 and less than or equal to 1; E is one of boron, magnesium, aluminum, gallium and transition metallic elements except Mn; and m is more than or equal to 0.9 and less than or equal to 1.1, n is more than or equal to 0 and less than or equal to 1, and j is more than 1 and less than 6. 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
With lithium intercalation compound as the lithium secondary battery of positive active material because of have cell voltage height, specific energy large, have extended cycle life, the advantage such as self discharge is little, in various portable type electronic products and communication tool, be used widely, and progressively be developed to the cleaning power source of electric automobile.
Present LiCoO as cathode active material for lithium secondary battery
2The advantage such as high because of open circuit voltage, that specific capacity large, have extended cycle life, extensive use, but because cobalt resource is few, expensive and certain toxicity is arranged, thereby use and be subject to certain limitation; Spinelle LiMn
2O
4Because at high temperature the cycle charge discharge capacitance fall-off is fast, and LiNiO
2Because synthetic difficulty and have the problem of fail safe is so both use not yet in a large number at present for both.
LiFePO with olivine structural
4Being found can be used as active substance of lithium ion battery anode from 1997 is just paid attention to widely; It has stably discharge voltage plateau about 3.4V, and raw material sources extensively, Heat stability is good, theoretical capacity be high, environmentally friendly, but pure LiFePO
4Electron conductivity lower, the present common LiFePO that improves
4The method of electron conductivity have at LiFePO
4Middle Li doped CoO
2Deng and form new positive active material, although the electronic conductivity of this positive active material increases, its electronic conductivity is still lower, generally only is 10
-6S/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
XxM '
Yy(XO
4)
Zz, LiM ' XO
5, LiM ' XO
6, LiM ' X
2O
7In the compound of expression one or more, 0＜xx/zz≤1,0＜yy/zz≤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 LiD
cO
2, Li
iNi
1-d-eCo
dMn
eO
2, LiNi
1-f-gCo
fAl
gO
2, Li
xNi
1-yCoO
2And Li
mMn
2-nE
nO
jIn the compound of expression one or more, wherein, D is a kind of among B, Mg, Al, Ti, Cr, Fe, Cu, Zn, Ga, Y, La, the V, 0＜c≤3; 0.9≤i≤1.2,0≤d≤0.5,0＜e≤0.3; 0≤f≤0.5,0≤g≤0.3; 0.9≤x≤1.1,0≤y≤1; E is a kind of in boron, magnesium, aluminium, gallium and the transition metal except Mn, 0.9≤m≤1.1,0≤n≤1,1＜j＜6.
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 only is 1.5 * 10 by the electronic conductivity of the positive active material that simply is mixed to get
-6S/cm, the electronic conductivity of the positive active material that makes by the embodiment of the invention 2 then are 0.24S/cm, the latter for the former 160000 times; Comparative Examples 2 only is 2.4 * 10 by the electronic conductivity of the positive active material that simply is mixed to get
-5S/cm, the electronic conductivity of the positive active material that makes by the embodiment of the invention 3 then are 0.6S/cm, the latter for the former 25000 times.
In addition, data from table 2 of the present invention can be found out, the initial discharge specific discharge capacity of the battery A1-A14 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-AC2 of Comparative Examples, in the identical situation of other condition, the specific discharge capacity of the battery A2 that the positive active material that is made by method provided by the invention is made is 124 MAh/gs, and reference cell AC1 then only is 108 MAh/gs; Capacity dimension holdup after the battery A2 circulation 500 times is 95.90%, and the capacity dimension holdup after the reference cell AC1 circulation 500 times only is 88.21%; The specific discharge capacity of the battery A3 that the positive active material that is made by method provided by the invention is made is 126 MAh/gs, and reference cell AC2 then only is 112 MAh/gs; Capacity dimension holdup after the battery A3 circulation 500 times is 96.67%, and the capacity dimension holdup after the reference cell AC2 circulation 500 times only is 90.09%; 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 5 preparations;
Fig. 5 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
XxM '
Yy(XO
4)
Zz, LiM ' XO
5, LiM ' XO
6, LiM ' X
2O
7In the compound of expression one or more, 0＜xx/zz≤1,0＜yy/zz≤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 LiD
cO
2, Li
iNi
1-d-eCo
dMn
eO
2, LiNi
1-f-gCo
fAl
gO
2, Li
xNi
1-yCoO
2And Li
mMn
2-nE
nO
jIn the compound of expression one or more, wherein, D is a kind of among B, Mg, Al, Ti, Cr, Fe, Cu, Zn, Ga, Y, La, the V, 0＜c≤3; 0.9≤i≤1.2,0≤d≤0.5,0＜e≤0.3; 0≤f≤0.5,0≤g≤0.3; 0.9≤x≤1.1,0≤y≤1; E is a kind of in boron, magnesium, aluminium, gallium and the transition metal except Mn, 0.9≤m≤1.1,0≤n≤1,1＜j＜6.
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 0.001-10S/cm, is preferably 0.01-2S/cm.
Wherein, in lithium atom, the mol ratio of described raw material one and raw material two can be 1: 0.01-0.05.
Among the present invention, general formula Li
XxM '
Yy(XO
4)
ZzRepresented 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 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 '.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 Li
mMn
2-nE
nO
jIn E represent a kind of in boron, magnesium, aluminium, gallium and the transition metal except Mn, described transition metal can be titanium, chromium, iron, cobalt, nickel, copper, zinc or yttrium etc., described raw material two can be LiCoO
2, LiNiO
2, LiMn
2O
4, LiVO
2, Li
1.03Ni
0.77Co
0.1Mn
0.1O
2, LiNi
0.8Co
0.15Al
0.05O
2, LiMnBO
3In one or more.
According to the present invention, under the preferable case, described mixture can also contain carbon source, the consumption of carbon source so that in the positive active material that generates 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, as long as can form carbon behind the sintering, 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 speed of intensification can be 5-20 ℃/min, and the temperature of sintering can be 500-850 ℃, and the time of sintering can be 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.
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 can for the 0.01-8 % by weight of positive active material, be 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 the conductive agent that positive active material, adhesive and selectivity contain is 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.
Embodiment 1
With LiFePO
4And LiNiO
2Mixing according to 1: 0.02 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And LiNiO
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/ LiNiO
2The mixed crystal of/C.
Embodiment 2
With LiFePO
4And LiCoO
2Mixing according to 1: 0.04 ratio of mol ratio, is that the amount of 2 % by weight adds the acetylene 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 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/ LiCoO
2The 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 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 LiCoO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And LiCoO
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/ LiCoO
2The mixed crystal of/C.
Comparative Examples 1
With LiFePO
4And LiCoO
2Mixing according to 1: 0.04 ratio of mol ratio, is that the amount of 2 % by weight adds the acetylene black as carbon source according to the content of carbon in the positive active material that generates then, and ball milling 10 hours mixes, wherein LiFePO
4And LiCoO
2Respectively with the LiFePO of embodiment 2
4And LiCoO
2It is identical to originate; The mixture that ball milling is good namely obtains by LiFePO 80 ℃ of oven dry
4, LiCoO
2Positive active material with the carbon composition.
Embodiment 3
With LiFePO
4, LiMn
2O
4And LiVO
2According to 1: 0.03: 0.01 ratio ball milling of mol ratio 10 hours, mix; 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/ LiMn
2O
4/ LiVO
2Mixed 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 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
4, LiMn
2O
4And LiVO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4, LiMn
2O
4And LiVO
2Still exist with three-phase structure, do not have new material and generate, the positive active material that has proved thus above-mentioned preparation is LiFePO
4/ LiMn
2O
4/ LiVO
2Mixed crystal.
Comparative Examples 2
With LiFePO
4, LiMn
2O
4And LiVO
2According to 1: 0.03: 0.01 ratio ball milling of mol ratio 10 hours, mix, wherein LiFePO
4, LiMn
2O
4And LiVO
2Respectively with the LiFePO of embodiment 3
4, LiMn
2O
4And LiVO
2It is identical to originate; The mixture that ball milling is good namely obtains by LiFePO 80 ℃ of oven dry
4, LiMn
2O
4And LiVO
2The positive active material that forms.
Embodiment 4
With LiOH, Ni (OH)
2, Co
2O
3, Al
2O
3Take mol ratio as 1: 0.8: 0.075: 0.025 ratio is mixed, and ball milling 5 hours is warming up to 800 ℃ of roastings 15 hours with 7 ℃/min under oxygen 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 LiNi
0.8Co
0.15Al
0.05O
2Standard diagram is compared, thereby confirms that this sintered product is LiNi
0.8Co
0.15Al
0.05O
2
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned LiNi that makes
0.8Co
0.15Al
0.05O
2Replace LiNiO
2, make positive active material LiFePO
4/ LiNi
0.8Co
0.15Al
0.05O
2The 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 LiFePO
4And LiNi
0.8Co
0.15Al
0.05O
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And LiNi
0.8Co
0.15Al
0.05O
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/ LiNi
0.8Co
0.15Al
0.05O
2The mixed crystal of/C.
Embodiment 5
With LiOH, Ni (OH)
2, Co
2O
3, MnO
2Take mol ratio as 1.03: 0.77: 0.05: 0.1 ratio is mixed, and ball milling 5 hours is warming up to 800 ℃ of roastings 15 hours with 7 ℃/min under oxygen 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 Li
1.03Ni
0.77Co
0.1Mn
0.1O
2Standard diagram is compared, thereby confirms that this sintered product is Li
1.03Ni
0.77Co
0.1Mn
0.1O
2
Prepare positive active material according to embodiment 1 described method, different is, with the above-mentioned Li that makes
1.03Ni
0.77Co
0.1Mn
0.1O
2Replace LiNiO
2, make positive active material LiFePO
4/ Li
1.03Ni
0.77Co
0.1Mn
0.1O
2The 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 4, in the diffraction maximum of the positive active material that as can be seen from Figure 4 behind above-mentioned sintering, makes, except LiFePO
4And Li
1.03Ni
0.77Co
0.1Mn
0.1O
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And Li
1.03Ni
0.77Co
0.1Mn
0.1O
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/ Li
1.03Ni
0.77Co
0.1Mn
0.1O
2The mixed crystal of/C.
Embodiment 6
Prepare positive active material according to embodiment 1 described method, different is to use LiMnBO
3Replace LiNiO
2, make positive active material LiFePO
4/ LiMnBO
3The 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 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 LiMnBO
3Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiFePO in this positive active material be described
4And LiMnBO
3Still 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/ LiMnBO
3The mixed crystal of/C.
Embodiment 7
" 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained Li in this positive active material be described
0.99Y
0.01FePO
4And LiNiO
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 Li
0.99Y
0.01FePO
4/ LiNiO
2The mixed crystal of/C.
Embodiment 8
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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiTi in this positive active material be described
0.05Fe
0.95PO
4And LiNiO
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 LiTi
0.05Fe
0.95PO
4/ LiNiO
2The 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 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiNi in this positive active material be described
0.1Fe
0.9PO
4And LiNiO
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 LiNi
0.1Fe
0.9PO
4/ LiNiO
2The mixed crystal of/C.
Adopt embodiment 9 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiCo in this positive active material be described
0.01Fe
0.99PO
4And LiNiO
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 LiCo
0.01Fe
0.99PO
4/ LiNiO
2The mixed crystal of/C.
Embodiment 11
Adopt embodiment 9 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiMn in this positive active material be described
0.02Fe
0.98PO
4And LiNiO
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 LiMn
0.02Fe
0.98PO
4/ LiNiO
2The mixed crystal of/C.
Embodiment 12
Adopt embodiment 9 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiMg in this positive active material be described
0.03Fe
0.97PO
4And LiNiO
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 LiMg
0.03Fe
0.97PO
4/ LiNiO
2The mixed crystal of/C.
Embodiment 13
Adopt embodiment 9 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiCa in this positive active material be described
0.05Fe
0.95PO
4And LiNiO
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 LiCa
0.05Fe
0.95PO
4/ LiNiO
2The mixed crystal of/C.
Embodiment 14
Adopt embodiment 9 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/ LiNiO
2The 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 LiNiO
2Characteristic peak outside, do not find the New Characteristics peak, thereby contained LiZn in this positive active material be described
0.07Fe
0.93PO
4And LiNiO
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 LiZn
0.07Fe
0.93PO
4/ LiNiO
2The mixed crystal of/C.
The electronic conductivity test of positive active material
The positive active material that under 25 ℃ embodiment 1-14 and Comparative Examples 1-2 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 1-14 and Comparative Examples 1-2 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 active material |
| Embodiment 1 | 0.03 |
| Embodiment 2 | 0.24 |
| Comparative Examples 1 | 1.5×10 -6 |
| Embodiment 3 | 0.6 |
| Comparative Examples 2 | 2.4×10 -5 |
| Embodiment 4 | 1.8 |
| Embodiment 5 | 1.2 |
| Embodiment 6 | 0.81 |
| Embodiment 7 | 0.64 |
| Embodiment 8 | 0.57 |
| Embodiment 9 | 0.95 |
| |
0.68 |
| Embodiment 11 | 0.43 |
| Embodiment 12 | 0.91 |
| Embodiment 13 | 0.76 |
| Embodiment 14 | 0.34 |
Embodiment 15-28 and Comparative Examples 3-4
(1) anodal preparation
The positive active material that respectively 90 grams is made by embodiment 1-14 and Comparative Examples 1-2,5 gram adhesive Kynoar (PVDF) and 5 gram conductive agent acetylene blacks join in the 50 gram 1-METHYLPYRROLIDONEs, then stir in de-airing mixer and form 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 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.
(3) assembling of battery
Respectively above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol/L is dissolved in EC/EMC/DEC=1: form nonaqueous electrolytic solution in the mixed solvent of 1: 1 (volume ratio), this electrolyte is injected battery aluminum shell with the amount of 3.8g/Ah, lithium rechargeable battery A1-A14, AC1-AC2 are made respectively in sealing.
The performance test of battery
The above-mentioned lithium ion battery A1-A14 that makes and AC1-AC2 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 15 | A1 | 121 | 95.01％ |
| Embodiment 16 | A2 | 124 | 95.90％ |
| Comparative Examples 3 | AC1 | 108 | 88.21％ |
| Embodiment 17 | A3 | 126 | 96.67％ |
| Comparative Examples 4 | AC2 | 112 | 90.09％ |
| Embodiment 18 | A4 | 135 | 98.87％ |
| Embodiment 19 | A5 | 131 | 97.56 |
| Embodiment | |||
| 20 | A6 | 128 | 97.07％ |
| Embodiment 21 | A7 | 126 | 96.77％ |
| Embodiment 22 | A8 | 126 | 96.47％ |
| Embodiment 23 | A9 | 129 | 97.27％ |
| Embodiment 24 | A10 | 125 | 96.81％ |
| Embodiment 25 | A11 | 124 | 96.27％ |
| Embodiment 26 | A12 | 129 | 97.26％ |
| Embodiment 27 | A13 | 127 | 96.73％ |
| Embodiment 28 | A14 | 124 | 96.09％ |
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 only is 1.5 * 10 by the electronic conductivity of the positive active material that simply is mixed to get
-6S/cm, the electronic conductivity of the positive active material that makes by the embodiment of the invention 2 then are 0.24S/cm, the latter for the former 160000 times; Comparative Examples 2 only is 2.4 * 10 by the electronic conductivity of the positive active material that simply is mixed to get
-5S/cm, the electronic conductivity of the positive active material that makes by the embodiment of the invention 3 then are 0.6S/cm, the latter for the former 25000 times.
In addition, data from above-mentioned table 2 can be found out, the initial discharge specific discharge capacity of the battery A1-A14 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-AC2 of Comparative Examples, in the identical situation of other condition, the specific discharge capacity of the battery A2 that the positive active material that is made by method provided by the invention is made is 124 MAh/gs, and reference cell AC1 then only is 108 MAh/gs; Capacity dimension holdup after the battery A2 circulation 500 times is 95.90%, and the capacity dimension holdup after the reference cell AC1 circulation 500 times only is 88.21%; The specific discharge capacity of the battery A3 that the positive active material that is made by method provided by the invention is made is 126 MAh/gs, and reference cell AC2 then only is 112 MAh/gs; Capacity dimension holdup after the battery A3 circulation 500 times is 96.67%, and the capacity dimension holdup after the reference cell AC2 circulation 500 times only is 90.09%; 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 (9)
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 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, described raw material two is LiVO
2, LiMnBO
3In one or more; Product behind raw material one and raw material two sintering is mixed crystal.
2. the preparation method of positive active material according to claim 1, wherein, in lithium atom, 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 one is LiFePO
4, Li
0.99Y
0.01FePO
4And LiR
iFe
1-iPO
4In the compound of expression one or more.
4. the preparation method of the described positive active material of any one according to claim 1-3, wherein, described mixture also contains carbon source, the consumption of described carbon source so that in the positive active material that generates 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.
5. the preparation method of positive active material according to claim 4, wherein, described carbon black is acetylene black.
6. the preparation method of positive active material according to claim 1, wherein, the condition of described sintering comprises that the speed of intensification is 5-20 ℃/min, and the temperature of sintering is 500-850 ℃, and the time of sintering is 5-32 hour.
7. a positive active material is characterized in that, this positive active material is made by the described method of any one among the claim 1-6.
8. 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 7.
9. 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 described positive pole just very claimed in claim 8.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101892392A CN101740751B (en) | 2008-11-07 | 2008-12-26 | Method for preparing anode active substance, anode active substance, anode and battery |
| PCT/CN2009/074773 WO2010051748A1 (en) | 2008-11-07 | 2009-11-03 | Cathode active material, lithium ion secondary battery and rechargeable battery having the same |
| PCT/CN2009/074770 WO2010051747A1 (en) | 2008-11-07 | 2009-11-03 | Method of preparing cathode active material and method of forming lithium ion secondary battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810173688.8 | 2008-11-07 | ||
| CN200810173688 | 2008-11-07 | ||
| CN2008101892392A CN101740751B (en) | 2008-11-07 | 2008-12-26 | Method for preparing anode active substance, anode active substance, anode and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101740751A CN101740751A (en) | 2010-06-16 |
| CN101740751B true CN101740751B (en) | 2013-04-10 |
Family
ID=42463858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101892392A Active CN101740751B (en) | 2008-11-07 | 2008-12-26 | Method for preparing anode active substance, anode active substance, anode and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101740751B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904301B (en) | 2014-02-26 | 2016-11-23 | 江苏华东锂电技术研究院有限公司 | The preparation method of anode active material of lithium ion battery |
| CN105655567B (en) * | 2016-04-14 | 2018-10-02 | 天津巴莫科技股份有限公司 | Phosphoric acid vanadium lithium/cobalt-lithium oxide composite material and preparation method |
| CN106159241A (en) * | 2016-08-31 | 2016-11-23 | 四川剑兴锂电池有限公司 | A kind of anode pole piece and the amorphous carbon lithium battery containing this positive plate |
| CN106783166B (en) * | 2016-12-23 | 2019-05-17 | 武汉昊诚能源科技有限公司 | A kind of preparation method of high power pulse battery capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1725533A (en) * | 2004-07-19 | 2006-01-25 | 肇庆市风华锂电池有限公司 | Lithium ion secondary battery plus plate active material and its preparation process |
| CN101288197A (en) * | 2004-12-28 | 2008-10-15 | 波士顿电力公司 | Lithium-ion secondary battery |
-
2008
- 2008-12-26 CN CN2008101892392A patent/CN101740751B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1725533A (en) * | 2004-07-19 | 2006-01-25 | 肇庆市风华锂电池有限公司 | Lithium ion secondary battery plus plate active material and its preparation process |
| CN101288197A (en) * | 2004-12-28 | 2008-10-15 | 波士顿电力公司 | Lithium-ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101740751A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101478041B (en) | Positive pole active substance, positive pole and battery | |
| CN101478042B (en) | Positive pole active substance, positive pole and battery | |
| JP7232356B2 (en) | rechargeable battery cell | |
| US8052897B2 (en) | Composite compound with mixed crystalline structure | |
| JP5221660B2 (en) | Battery negative electrode and lithium ion battery using the same | |
| JP6188158B2 (en) | Negative electrode for lithium ion secondary battery, negative electrode slurry for lithium ion secondary battery, and lithium ion secondary battery | |
| CN102487151B (en) | Lithium ion secondary battery | |
| CN103050694B (en) | A kind of positive electrode active materials and preparation method thereof, battery | |
| CN106571446A (en) | Anode active material, method for producing same, and lithium secondary battery | |
| KR20120056674A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| CN101286561A (en) | Negative electrode active material, preparation method thereof and rechargeable lithium battery comprising same | |
| JP2008091236A (en) | Nonaqueous electrolyte secondary battery | |
| CN101515644A (en) | Anode active substance, method for preparing same and lithium ion battery containing same | |
| CN109802102B (en) | Positive active material for rechargeable lithium battery, rechargeable lithium battery including the same, and battery module including the same | |
| CN103367795B (en) | Lithium rechargeable battery | |
| CN101734636B (en) | Method for preparing anode active substance, anode active substance, anode and battery | |
| JP2016154137A (en) | Battery positive electrode material and lithium ion battery | |
| CN109309207A (en) | A kind of positive active material and preparation method thereof, anode and lithium ion battery | |
| CN101740751B (en) | Method for preparing anode active substance, anode active substance, anode and battery | |
| CN101197436A (en) | Positive plate of lithium ion secondary battery, and battery including the same | |
| CN109980221B (en) | A high-voltage lithium-ion battery positive electrode material and its preparation method and application | |
| CN103178265A (en) | Positive active material, method of preparing the same, and rechargeable lithium battery | |
| JP2014216211A (en) | Electrode and nonaqueous secondary battery | |
| JP2002175836A (en) | Nonaqueous electrolyte battery | |
| KR101352836B1 (en) | Process for Preparing Lithium Manganese-Based Oxide of Li-excess Content and Lithium Secondary Battery Comprising the Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |