CN101740749A - 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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- CN101740749A CN101740749A CN200810189233A CN200810189233A CN101740749A CN 101740749 A CN101740749 A CN 101740749A CN 200810189233 A CN200810189233 A CN 200810189233A CN 200810189233 A CN200810189233 A CN 200810189233A CN 101740749 A CN101740749 A CN 101740749A
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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 comprises a lithium source, an iron source and a phosphorus source; and the raw material 2 is one or more of compounds represented by a general formula: AaMbNcOd, wherein A, M, N are different from each other, which are IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIII group metallic elements respectively; a is more than or equal to 0 and less than or equal to 6, b is more than or equal to 0 and less than or equal to 6, c is more than 0 and less than or equal to 6, d is more than 0 and less than o equal to 12, and a and b are not simultaneously 0; and due to the sintering condition, the prepared anode active substance comprises a lithium ferrous phosphate crystal. The battery made of the anode active substance prepared by the method provided by the invention has good specific capacity of quality and good cycle performance.
Description
Technical field
The invention relates to a kind of preparation method of positive active material and the positive active material that makes by this preparation method and the positive pole that comprises this positive active material and comprise the battery that this is anodal, especially positive active material and the positive pole that comprises this positive active material that 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 big, self discharge is little, has extended cycle life, in light weight and advantages of environment protection becomes portable type electronic product.Therefore lithium secondary battery and associated materials thereof have become one of research focus of countries in the world scientific research personnel.Wherein positive active material becomes the restriction lithium secondary battery by the bottleneck of large-scale application owing to specific capacity on the high side is on the low side.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 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, make polyanion type compound-material have 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 section bar 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, can carry out a large amount of lithium secondaries and take off embedding, and this point and the metal oxide of the second generation have bigger different; The second, be easy to the discharge potential platform of modulation material.But the shortcoming of polyanion section bar material is that conductance is lower, thereby makes the specific discharge capacity of the battery that made by polyanion section bar material lower, cycle performance is relatively poor.Method to material modification mostly is material to be carried out methods such as carbon coating or doping high-valency metal to improve its electronic conductivity at present, but it is not ideal to improve effect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new positive active material and the positive active material and the positive pole that comprises this positive active material that are made by this preparation method and comprise the battery that this is anodal, the specific discharge capacity of the battery that the positive active material that this method makes is made and cycle performance are all better.
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 contains lithium source, source of iron and phosphorus source, and 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 II A, HIA, IVA, V A, I B, II B, 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; Described lithium source is for containing the lithium material with source of iron, phosphorus source sintering obtain LiFePO 4, and the condition of described sintering makes and contains the ferrous phosphate crystalline lithium in the positive active material that makes.
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 a 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 as can be seen, the electronic conductivity of the positive active material that method provided by the invention makes can reach the height of 0.175-1.8S/cm.In addition, data from table 2 of the present invention as can be seen, the initial discharge specific discharge capacity of the 0.5C of the positive active material that is made by method provided by the invention and the battery A1-A6 that makes is at 123 MAHs/more than the gram, capacity sustainment rate after the battery circulation 500 times is more than 95%, illustrated that thus the specific discharge capacity and the cycle performance of the battery that the positive active material that made by method provided by the invention is made is all better.
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 contains lithium source, source of iron and phosphorus source, and 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 II A, IIIA, IVA, V A, I B, II B, 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; Described lithium source is for containing the lithium material with source of iron, phosphorus source sintering obtain LiFePO 4, and the condition of described sintering makes and contains the ferrous phosphate crystalline lithium in the positive active material that makes.
Product behind raw material one of the present invention and raw material two sintering is a mixed crystal, described mixed crystal is meant the mixed crystal that two or more compound forms through oversintering, chemical reaction does not take place between this two or more the compound, but electronic conductivity with obvious raising, its mechanism may be interpreted as: between this two or more the compound chemical reaction does not take place, but in the process of sintering, but introduced a large amount of crystal defects, changed the electronics bonding state between the compound, made 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, make the electronic conductivity of this mixed crystal be 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 consumption in described lithium source, source of iron and phosphorus source makes that preferably the mol ratio of Fe: Li: P is 1 in the described raw material one: 0.95-1.1: 0.95-1.1; In lithium atom, the lithium source in the described raw material one and the mol ratio of 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 than the ratio of mol ratio A: M: N=a: b: c at 400-1000 ℃ of following 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.
Concrete, 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.
Described lithium source can be for well known to a person skilled in the art various lithiums source, for example can be in lithium hydroxide, the various lithium salts one or more, and described lithium salts can be various inorganic lithium salts and/or organic lithium salt.Concrete, described lithium salts can be one or more in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate.
Described source of iron can be for well known to a person skilled in the art various sources of iron, for example can be the hydroxide of the oxide of various iron, iron, in the various molysite one or more, and described molysite can be various inorganic molysites and/or organic molysite.Concrete, described source of iron can be one or more in ferrous oxalate, ferrous carbonate, ferric acetate, di-iron trioxide, ferric phosphate, ferric pyrophosphate, the ferric nitrate.
Described phosphorus source can be for well known to a person skilled in the art various phosphorus source, for example can be in phosphoric acid and/or the phosphate one or more, be preferably in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ferric phosphate, phosphoric acid, the lithium dihydrogen phosphate one or more.
Under the preferable case, also contain carbon source in the described raw material one, the content of carbon is 1-5 weight % in the feasible positive active material that generates of the consumption of described carbon source.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.
When described source of iron was the divalence source of iron, the condition of described sintering comprised that the atmosphere of sintering is inert atmosphere or reducing atmosphere, and heating rate can be 5-20 ℃/min, and sintering temperature can be 500-850 ℃, and sintering time can be 5-32 hour.
When described source of iron was ferric iron source, the condition of described sintering comprised that the atmosphere of sintering is reducing atmosphere, and heating rate can be 5-20 ℃/min, and sintering temperature can be 500-850 ℃, and sintering time can be 5-32 hour.Described reducing atmosphere can realize by feeding various reducibility gas, also can generate by the original position in sintering process of the carbon source in the reaction raw materials and realize.The amount of reducing atmosphere can be selected in a big way, as long as can make described ferric iron fully be reduced into ferrous iron.
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 a 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 that will prepare and cathode size and the requirement of operability are adjusted flexibly to this concentration, the concentration of for example described hydrophilic adhesive solution can be 0.5-4 weight %, and the concentration of described hydrophobicity adhesive agent emulsion can be 10-80 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 weight % of positive active material, is preferably 1-5 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 weight % of described positive electrode total weight is preferably 2-10 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 positive active material, adhesive and conductive agent are prepared into anode sizing agent with solvent, 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 all kinds of solvents that uses in the prior art, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.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 the anode sizing agent that will prepare 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 40-90 weight % that the consumption of this solvent makes the content of positive active material in the anode sizing agent, is preferably 50-85 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-graphitized charcoal, graphite or the charcoal that obtained by high-temperature oxydation by polyyne family macromolecule material, also can use other material with carbon element for example pyrolytic carbon, coke, organic polymer sinter, active carbon etc.Described organic polymer sinter can be by the product with gained after sintering such as phenolic resins, epoxy resin and the charing.
Described adhesive can be selected from the adhesive of lithium secondary battery routine, 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 weight % of negative electrode active material, is preferably 2-5 weight %.
Under the preferable case, described negative material can also contain conductive agent.Because conductive agent is used to increase 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, for example, are benchmark with the negative material, and the content of conductive agent is generally 0.1-12 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 the conductive agent that negative electrode active material, adhesive and selectivity contain is prepared into cathode size with solvent, 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 all kinds of solvents that uses in the prior art, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.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 the cathode size that will prepare 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 40-90 weight % that the consumption of this solvent makes the content of negative electrode active material in the cathode size, is preferably 50-85 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 acid 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), carbonic acid first propyl ester (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, is preferably the 0.8-1.2 mol.
The preparation method of lithium secondary battery provided by the invention can be a 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, sealing obtains lithium secondary battery then.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
5With mol ratio is 1: 1: 1 mixed, and 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 lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate is Fe: Li: P=1 with the mol ratio: 1: 1 mixed is even, then with lithium carbonate and MnTiNb
2O
8Mol ratio be that 1: 0.04 ratio (in lithium atom) adds the above-mentioned MnTiNb that makes
2O
8And the content according to carbon in the positive active material that generates is the starch of the amount adding of 5 weight % as carbon source, ball milling 10 hours, the mixture that ball milling is good is 80 ℃ of oven dry, then dried powder is warming up to 600 ℃ with 10 ℃/min under nitrogen atmosphere, carries out the constant temperature sintering and obtained positive active material in 20 hours.
Embodiment 2
With ZnO, Ta
2O
5With mol ratio is 1: 1 mixed, and 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 lithium oxalate, di-iron trioxide, diammonium hydrogen phosphate is Fe: Li: P=1 with the mol ratio: 0.95: 1.1 mixed is even, then with lithium oxalate and ZnTa
2O
6Mol ratio be that 1: 0.03 ratio (in lithium atom) adds the above-mentioned ZnTa that makes
2O
6, ball milling 10 hours, the mixture that ball milling is good be 80 ℃ of oven dry, then with dried powder at H
2-CO-N
2(volume ratio of this each gas componant is H
2: CO: N
2=0.05: 0.15: 0.8) is warming up to 500 ℃ with 5 ℃/min under the reducing atmosphere, carries out the constant temperature sintering and obtained positive active material LiFePO in 30 hours
4/ ZnTa
2O
6Mixed crystal.
The XRD diffraction pattern that adopts 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, as can be seen from Figure 2 in the diffraction maximum of the positive active material that behind above-mentioned sintering, makes, except LiFePO
4And ZnTa
2O
6Characteristic peak outside, do not find new characteristic 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 above-mentioned preparation thus is LiFePO
4/ ZnTa
2O
6Mixed crystal.
Embodiment 3
With Y
2O
3, BaCO
3, TiO
2With mol ratio is 0.5: 3: 2 mixed, and 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
2O
8.5Standard diagram is compared, thereby confirms that this sintered product is YBa
3Ti
2O
8.5
With lithium hydroxide, ferrous carbonate, phosphoric acid is Fe: Li: P=1 with the mol ratio: 1.1: 0.95 mixed is even, then with lithium hydroxide and YBa
3Ti
2O
8.5Mol ratio be that 1: 0.02 ratio (in lithium atom) adds the above-mentioned YBa that makes
3Ti
2O
8.5And the content according to carbon in the positive active material that generates is the carbon black of the amount adding of 2 weight % as carbon source, ball milling 10 hours, the mixture that ball milling is good is 80 ℃ of oven dry, then dried powder is warming up to 800 ℃ with 20 ℃/min under nitrogen atmosphere, carries out the constant temperature sintering and obtained positive active material LiFePO in 8 hours
4/ YBa
3Ti
2O
8.5The mixed crystal of/C.
The XRD diffraction pattern that adopts 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, as can be seen from Figure 3 in the diffraction maximum of the positive active material that behind above-mentioned sintering, makes, except LiFePO
4And YBa
3Ti
2O
8.5Characteristic peak outside, do not find new characteristic 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 above-mentioned preparation thus is LiFePO
4/ YBa
3Ti
2O
8.5The mixed crystal of/C.
Embodiment 4
With CuO, ZnO, Nb
2O
5With mol ratio is 0.85: 0.15: 1 mixed, and 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, with the above-mentioned Cu that makes
0.85Zn
0.15Nb
2O
6Replace MnTiNb
2O
8, make positive active material LiFePO
4/ Cu
0.85Zn
0.15Nb
2O
6The 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 as can be seen from the figure in the diffraction maximum of the positive active material that makes behind above-mentioned sintering, except LiFePO
4And Cu
0.85Zn
0.15Nb
2O
6Characteristic peak outside, do not find new characteristic peak, thereby contained LiFePO 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 above-mentioned preparation thus is LiFePO
4/ Cu
0.85Zn
0.15Nb
2O
6The mixed crystal of/C.
Embodiment 5
With ZrO
2, TiO
2, SnO
2With mol ratio is 0.75: 0.75: 0.5 mixed, and 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.
The XRD diffraction pattern that adopts this positive electrode that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 4, as can be seen from Figure 4 in the diffraction maximum of the positive active material that behind above-mentioned sintering, makes, except LiFePO
4And Zr
0.75Ti
0.75Sn
0.5O
4Characteristic peak outside, do not find new characteristic 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 above-mentioned preparation thus is LiFePO
4/ Zr
0.75Ti
0.75Sn
0.5O
4The mixed crystal of/C.
Embodiment 6
With FeO, WO
3With mol ratio is 1: 1 mixed, and 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.
The XRD diffraction pattern that adopts this positive electrode that the D/MAX-2200/PC type x-ray powder diffraction instrument of Rigaku company records as shown in Figure 5, as can be seen from Figure 5 in the diffraction maximum of the positive active material that behind above-mentioned sintering, makes, except LiFePO
4And FeWO
4Characteristic peak outside, do not find new characteristic 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 above-mentioned preparation thus is LiFePO
4/ FeWO
4The mixed crystal of/C.
The electronic conductivity test of positive active material
The positive active material that under 25 ℃ embodiment 1-6 is made depresses to cylinder in the briquetting pressure of 30MPa respectively, measure this cylindrical height l, bottom surface diameter d and resistance R then respectively, calculate the electronic conductivity σ of embodiment 1-6 positive active material, σ=4l/ (π Rd respectively 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 |
| Embodiment 4 | ??1.2 |
| Embodiment 5 | ??1.5 |
| Embodiment 6 | ??0.8 |
Embodiment 7-12
Preparation battery and test battery performance
(1) Zheng Ji preparation
The positive active material that 90 grams are made by embodiment 1-6 joins in the 50 gram N-methyl pyrrolidones with 5 gram adhesive Kynoar (PVDF) and 5 gram conductive agent acetylene blacks respectively, then the uniform anode sizing agent of stirring formation in de-airing mixer.This anode sizing agent is coated on the both sides that thickness is 20 microns aluminium foil equably, then in 150 ℃ of following oven dry, roll-in, cut to make and be of a size of 540 * 43.5 millimeters positive pole, wherein contain the anodal active components 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 N-methyl pyrrolidones, in de-airing mixer, stir then 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 following 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 secondary battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/EMC/DEC=1: form nonaqueous electrolytic solution in the mixed solvent of 1: 1 (volume ratio), this electrolyte is injected the battery aluminum hull with the amount of 3.8g/Ah, lithium secondary secondary cell A1-A6 is made in sealing respectively.
The performance test of battery
The above-mentioned lithium secondary battery A1-A6 that makes is placed on test respectively cashier's office in a shop, under 25 ℃ of conditions, carries out constant current charge with 0.5C earlier, be limited to 3.8 volts in the charging; 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 discharge capacity first of battery, and the specific discharge capacity of counting cell according to the following equation; The result is as shown in table 2 below.
Specific discharge capacity=battery is discharge capacity (MAH)/positive active material weight (gram) first
Repeat above-mentioned charging then, shelve, after the discharge step each 500 times, the discharge capacity of record battery.By the capacity sustainment rate after the following formula computation cycles 500 times.The capacity sustainment rate is big more, illustrates that then the cycle performance of battery is good more.The result is as shown in table 2 below.
Capacity sustainment rate=(the N time cyclic discharge capacity/discharge capacity) first * 100%
Table 2
| Numbering | The battery numbering | Specific discharge capacity (MAH/gram, 0.5C) | Capacity sustainment rate after 500 times circulates |
| Embodiment 7 | ??A1 | ??123 | ?95.21％ |
| Embodiment 8 | ??A2 | ??124 | ?95.87％ |
| Embodiment 9 | ??A3 | ??135 | ?98.87 |
| Embodiment | |||
| 10 | ??A4 | ??131 | ?97.56％ |
| Embodiment 11 | ??A5 | ??133 | ?98.50％ |
| Embodiment 12 | ??A6 | ??128 | ?97.05％ |
Data from above-mentioned table 1 as can be seen, the electronic conductivity of the positive active material that method provided by the invention makes can reach the height of 0.175-1.8S/cm.In addition, data from above-mentioned table 2 as can be seen, the initial discharge specific discharge capacity of the 0.5C of the positive active material that is made by method provided by the invention and the battery A1-A6 that makes is at 123 MAHs/more than the gram, capacity sustainment rate after the battery circulation 500 times is more than 95%, illustrated that thus the specific discharge capacity and the cycle performance of the battery that the positive active material that made by method provided by the invention is made is all better.
Claims (11)
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 contains lithium source, source of iron and phosphorus source, and 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; Described lithium source is for containing the lithium material with source of iron, phosphorus source sintering obtain LiFePO 4, and the condition of described sintering makes and contains the ferrous phosphate crystalline lithium in the positive active material that makes.
2. the preparation method of positive active material according to claim 1, wherein, the consumption in described lithium source, source of iron and phosphorus source makes that the mol ratio of Fe: Li: P is 1 in the described raw material one: 0.95-1.1: 0.95-1.1; In lithium atom, the lithium source in the described raw material one and the mol ratio of raw material two are 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 following sintering 8-15 hour.
4. according to the preparation method of any described positive active material among the claim 1-3, wherein, described raw material two is 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.
5. the preparation method of positive active material according to claim 1, wherein, described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium oxalate, the lithium acetate, described source of iron is one or more in ferrous oxalate, ferrous carbonate, ferric acetate, di-iron trioxide, ferric phosphate, ferric pyrophosphate, the ferric nitrate, and described phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, ferric phosphate, phosphoric acid, the lithium dihydrogen phosphate.
6. the preparation method of positive active material according to claim 1 wherein, also contains carbon source in the described raw material one.
7. the preparation method of positive active material according to claim 6, wherein, the consumption of described carbon source makes that the content of carbon is 1-5 weight % in the positive active material that generates; Described carbon source is one or more in carbon black, acetylene black, graphite, glucose, sucrose, citric acid, starch, dextrin, the polyethylene glycol.
8. 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.
9. a positive active material is characterized in that, this positive active material is made by any described method among the claim 1-8.
10. 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 the described positive active material of claim 9.
11. 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 10.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810189233A CN101740749A (en) | 2008-11-06 | 2008-12-26 | Method for preparing anode active substance, anode active substance, anode and 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 |
| PCT/CN2009/074774 WO2010051749A1 (en) | 2008-11-05 | 2009-11-03 | Method of preparing cathode active material and method of forming lithium secondary battery |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810175243.3 | 2008-11-06 | ||
| CN200810189233A CN101740749A (en) | 2008-11-06 | 2008-12-26 | Method for preparing anode active substance, anode active substance, anode and battery |
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|---|---|
| CN101740749A true CN101740749A (en) | 2010-06-16 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106847525A (en) * | 2016-12-23 | 2017-06-13 | 宁波中车新能源科技有限公司 | A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor and preparation method thereof |
| CN108277001A (en) * | 2018-02-24 | 2018-07-13 | 中山大学 | A kind of trivalent dysprosium ion applied to WLED devices adulterates single-matrix white fluorescent powder and preparation method thereof |
| CN110237847A (en) * | 2019-07-22 | 2019-09-17 | 清华大学 | Elctro-catalyst, electrode and its preparation method and application |
-
2008
- 2008-12-26 CN CN200810189233A patent/CN101740749A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106847525A (en) * | 2016-12-23 | 2017-06-13 | 宁波中车新能源科技有限公司 | A kind of asymmetric MnO of water system2/FeWO4Ultracapacitor and preparation method thereof |
| CN108277001A (en) * | 2018-02-24 | 2018-07-13 | 中山大学 | A kind of trivalent dysprosium ion applied to WLED devices adulterates single-matrix white fluorescent powder and preparation method thereof |
| CN108277001B (en) * | 2018-02-24 | 2020-08-07 | 中山大学 | Trivalent dysprosium ion doped single-matrix white fluorescent powder applied to W L ED device and preparation method thereof |
| CN110237847A (en) * | 2019-07-22 | 2019-09-17 | 清华大学 | Elctro-catalyst, electrode and its preparation method and application |
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