CN102208611A - Induced crystallization synthesis method for anode powder material of lithium ion secondary battery - Google Patents

Induced crystallization synthesis method for anode powder material of lithium ion secondary battery Download PDF

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CN102208611A
CN102208611A CN2011101016380A CN201110101638A CN102208611A CN 102208611 A CN102208611 A CN 102208611A CN 2011101016380 A CN2011101016380 A CN 2011101016380A CN 201110101638 A CN201110101638 A CN 201110101638A CN 102208611 A CN102208611 A CN 102208611A
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lithium ion
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王明月
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Abstract

The invention discloses an induced crystallization synthesis method for an anode powder material of a lithium ion secondary battery, which is characterized by comprising the following steps of: adding solid powder as a crystallization substrate into raw materials; mixing the materials uniformly; and calcining in an oxygen-containing atmosphere with the high temperature of 600-1100 DEG C at least once to obtain a final product, namely the anode powder material for the lithium ion secondary battery having a spinel structure as a main body. The method has the advantages of improving the crystallization characteristic and the doping evenness of the product, and the spinel structured anode material which has the characteristics of regular surfaces, high compacting density, low impurity content and the like has important economic significance and practical values for improving the performance of the lithium ion battery and promoting more extensive application of the lithium ion battery.

Description

A kind of induced crystallization synthetic method of lithium ion secondary battery positive electrode dusty material
(1) technical field:
The invention belongs to the new energy materials technical field, for lithium rechargeable battery provides a kind of positive powder powder material with high cyclical stability and excellent high temperature cyclic performance.
(2) background technology:
Lithium rechargeable battery is since being invented by Japanese Sony Corporation the nineties in last century, because have operating voltage height, energy density big, have extended cycle life, series of advantages such as memory-less effect, environmental protection, so obtained develop rapidly in fields such as portable electric appts such as cordless telephone, notebook computer, music player, digital cameras, become the main direction of secondary cell development.Energy crisis and environmental pollution make that searching is clean, reproducible secondary energy sources become the task of realizing that human social needs to be resolved hurrily; Simultaneously because the above-mentioned advantage of lithium rechargeable battery, as a kind of energy accumulating device, its application constantly enlarges and to large scale development.Have the not broken hair exhibition of using at present in fields such as electric bicycle, battery-operated motor cycle, electric tool, hybrid vehicle, pure electric vehicle, energy storage.
Positive electrode is one of the main member of lithium rechargeable battery and crucial decisive factor of performance quality.Present commercial lithium ion secondary battery anode material has the LiCoO of layer structure 2, Li (Ni, Co, Mn) O 2, Li (Ni, Co, Al) O 2, the LiMn of spinel structure 2O 4, and the LiFePO of olivine structural 4Deng.Wherein the positive electrode of layer structure has shortcomings such as fail safe is relatively poor, cost height; There are shortcomings such as conductivity is low, high rate performance difference in the positive electrode of olivine structural; And the LiMn of spinel structure 2O 4Positive electrode and modification derivant thereof then have resource extensively, cost is lower, voltage platform is high, charge-discharge performance is good, security performance is good, advantages of environment protection, is particularly one of the material of the tool prospect of power lithium ion battery of lithium ion battery of future generation.
The LiMn of present spinel structure 2O 4The synthetic method of positive electrode and modification derivant thereof generally has coprecipitation, sol-gel process, high temperature solid-state method etc.Wherein coprecipitation and sol-gel process are easy to realize the even mixing of metallic element on atomic level, have advantages such as synthesis temperature is low, pattern is good, chemical property is good, but also have a series of shortcomings such as synthesis technique complexity, cost height, product compacted density are low, suitability for industrialized production difficulty.And high temperature solid-state method is generally fired manganese compound and lithium compound after with the special ratios mixing and is formed in 700～850 ℃ temperature range because production operation simple, be easy to the first-selected production method that suitability for industrialized production etc. becomes the spinels positive electrode.But the material of above-mentioned conventional high-temperature solid phase method production has following deficiency generally speaking, be that the product crystallinity is poor, doping is inhomogeneous, the crystal surface pattern is irregular, compacted density is low, impurity content is high, and then cause that dissolving, electrolyte as metallic elements such as Mn decomposes under high potential, the instability of ginger-Taylor effect, material lattice etc. takes place during a stable condition, again and then cause that the product specific capacity is low, cycle life short when high temperature (especially cycle life), be made into a series of shortcomings such as energy density is low behind the battery.
(3) summary of the invention:
The object of the present invention is to provide a kind of induced crystallization synthetic method of lithium ion secondary battery anode dusty material, it can improve product crystallization property and implant uniformity, synthetic positive electrode with spinel structure of characteristics such as rule of surface, compacted density height, impurity content are low is to improving the lithium ion battery performance, promoting lithium ion battery and use more widely and have important economic implications and practical value.
A kind of induced crystallization synthetic method of lithium ion secondary battery anode dusty material is characterized in that may further comprise the steps:
(1) compares n by metal pantogen Li: (n Mn+ n M)=0.40～0.75 with lithium-containing compound, contain manganese compound, contain compound or fusing point one or more raw materials as crystal growth in the solid matter below 860 ℃ of doped chemical, adds pressed powder as crystalline matrix; The main body that is characterized as of described pressed powder has Li 1+xMn 2-y-zM zO 3-δThe composition general formula, wherein M is a doped chemical ,-1≤x≤1;-1≤y≤2; Y-x≤1; 0≤z≤0.75;-0.5≤δ≤0.5, δ is determined to keep electric neutrality by the valence state of metal ion;
(2) above-mentioned substance is evenly mixed or combination, obtain powder stock;
(3) in oxygen-containing atmosphere, after calcining at least once under 600～1100 ℃ the high temperature, obtaining end-product is that main body is the lithium ion secondary battery anode dusty material of spinel structure.
Lithium-containing compound is LiBO in the above-mentioned described step (1) 22H 2O, LiOHH 2O, Li 2CO 3, LiHCO 3, Li 2B 4O 75H 2O, Li 2SO 4H 2O, Li 2SiO 3, LiClH 2O, LiF, LiBrH 2O, LiNO 3, at least a in lithium formate, lithium acetate, lithium oxalate, ethanedioic acid hydrogen lithium, lithium salicylate, lithium tartrate, acid lithium tartrate or the lithium citrate.
Containing manganese compound in the above-mentioned described step (1) is MnOOH, Mn (OH) 2, MnO 2, MnCO 3, Mn 2O 3, Mn 3O 4, MnCl 24H 2O, MnF 2, MnBr 24H 2O, MnI 24H 2O, Mn (NO 3) 26H 2O, MnSO 44H 2At least a in O, manganese oxalate, formic acid manganese, manganese acetate or the manganese citrate.
Doped chemical in the above-mentioned described step (1) is at least a among Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Mo, W, Ni, Cu, Zn, Ba, Bi, Zr, Y, Sr, Ru, Rh, Pd, Cd, In, Sn, Sb, Ag, Pb, Ta, Hf, Re, Os, Ir, the Au.
Doped chemical in the above-mentioned described step (1) is at least a among Al, Ti, Cr, Co, Mo or the Ni.
The compound that contains doped chemical in the above-mentioned described step (1) is at least a in oxide, hydroxide, carbonate, subcarbonate, halide, sulphite, nitrate, oxalates, formates, acetate, salicylate or the citrate.
Fusing point is H at the solid matter below 860 ℃ in the above-mentioned described step (1) 3BO 3, B 2O 3, Li 2MoO 4, Li 2WO 4, Bi 2O 3In at least a.
Being characterized as of the middle pressed powder of above-mentioned described step (1): main body belongs to MnO-Li in the Li-Mn-O ternary phase diagrams 2MnO 3-MnO 2In-MnO the zone.
Being characterized as of the middle pressed powder of above-mentioned described step (1): main body belongs to MnO-Li in the Li-Mn-O ternary phase diagrams 2MnO 3-MnO 2III in the-MnO zone, IV zone.
Being characterized as of the middle pressed powder of above-mentioned described step (1): main body belongs to MnO-Li in the Li-Mn-O ternary phase diagrams 2MnO 3-MnO 2IV zone in the-MnO zone.
Being characterized as of pressed powder in the above-mentioned described step (1): agent structure belongs to cube, at least a in four directions or the rhombic system.
Being characterized as of the middle pressed powder of above-mentioned described step (1): agent structure is the cubic system that has same structure with product.
The middle particle diameter (D50) of pressed powder is 0.1～15 μ m in the above-mentioned described step (1).
The middle particle diameter (D50) of pressed powder is 0.3～0.8 times of a target end-product in the above-mentioned described step (1).
At least a processing that pressed powder injects or breaks up through surperficial coating, surface micro etching, ion in the above-mentioned described step (1).
Above-mentioned described surface micro etching is the low concentration acid corrosion that has added additive.
Above-mentioned described ion is injected under certain condition at least a in F, P, Cl, Si, S or the Se element has been mixed at least one class position of crystalline matrix in the above-mentioned three class positions of Mn lattice position, O lattice position, Mn lattice position and O lattice position.
Evenly mix in the above-mentioned described step (2) or combination is at least a in co-precipitation, pasty material parcel, ball milling, stirring, the concussion.
Above-mentioned described co-precipitation forms suspension solution for material in the step (1) is added in the entry, add alkaline aqueous solution control pH value and be 7.5～12.5 and carry out precipitation reaction, obtain the solid-liquid mixtures material, filter afterwards, washing, drying operation, obtain powder stock.
Above-mentioned described pasty material parcel forms suspension solution for material in the step (1) is added in the entry, behind the adding complexing agent aqueous solution, carry out drying 2～48h after 30～100 ℃ of continuous 1～24h of stirring form spawn, obtains powder stock.
Above-mentioned described ball-milling method is that material in the step (1) is added ball-milling additive, carries out drying behind ball milling 1～48h, obtains powder stock.
Above-mentioned described paddling process forms suspension solution for material in the step (1) is added in the entry, constantly being stirred to water at 80～100 ℃ evaporates fully, obtains powder stock.
Evenly mix in the above-mentioned described step (2) or in conjunction with the mutual spatial relationship of back material be granule center on bulky grain, bulky grain around granule, granule around bulky grain and bulky grain be that the growth of matrix covers around short grained intermediate state or with pressed powder as crystalline matrix.
Evenly mix in the above-mentioned described step (2) or be that granule centers on bulky grain or is that the growth of matrix covers with the pressed powder as crystalline matrix in conjunction with the mutual spatial relationship of back material.
The mutual spatial relationship of even mixing or combination back material is for the pressed powder as crystalline matrix being the growth covering of matrix in the above-mentioned described step (2).
End-product in the above-mentioned described step (3) is that main body is that the lithium ion secondary battery anode dusty material of spinel structure is LiMn 2O 4Or its modified product.
Above-mentioned described modification comprise the surface coat, bulk phase-doped, the surface coats and bulk phase-doped above-mentioned three kinds of modification mode at least a.
Mix above-mentioned described bulk phase-doped comprising at high proportion, has LiMn 1.4Cr 0.2Ni 0.4O 4, LiMnCoO 4And other similar substance all is regarded as LiMn 2O 4Doped derivatives at high proportion.
Superiority of the present invention is: the product that synthesizes according to production process of the present invention can improve product crystallization property and implant uniformity, have characteristics such as rule of surface, compacted density height, impurity content are low, to improving the lithium ion battery performance, promoting lithium ion battery and use more widely and have important economic implications and practical value.
(4) description of drawings:
Fig. 1-1 is lithium-manganese-oxygen ternary phase diagrams;
Fig. 1-2 is the amplification of Fig. 1-1 intermediate cam shape dash area, and wherein (I) zone is LiMn 3O 4-Mn 3O 4-MnO-LiMn 3O 4The part that is comprised, (II) zone is LiMn 3O 4-Mn 3O 4-LiMn 2O 4-Li 6.5Mn 5O 12-Li 4Mn 5O 12-Li 2MnO 3-LiMn 3O 4The part that is comprised, (III) zone is LiMn 2O 4-Mn 3O 4-MnO 2-LiMn 2O 4The part that is comprised, (IV) zone is LiMn 2O 4-Li 6.5Mn 5O 12-Li 4Mn 5O 12-MnO 2-LiMn 2O 4The part that is comprised, above-mentioned four zones exist overlapping at boundary;
Fig. 2 is that the X-ray diffraction spectrogram of synthetic sample in the execution mode compares;
Fig. 3 is that the discharge curve of synthetic sample in the execution mode compares;
Fig. 4 is that the cyclic curve of synthetic sample in the execution mode compares.
(5) embodiment:
Embodiment 1:
With particle diameter among the 550g (D50) is that the main body of 5.1 μ m is the Li of spinel structure 1.12Mn 1.90Co 0.10O 4.02Pressed powder is containing 5wt.% ammonium fluoride NH 4Submergence 15min in the 5wt.% phosphoric acid solution of F uses deionized water wash three times, 120 ℃ of oven dry 12h.With lithium acetate Li (CH 3COO) 2H 2O, manganese acetate Mn (CH 3COO) 24H 2O, cobalt acetate Co (CH 3COO) 24H 2O is by Li: Mn: the Co mol ratio is to be dissolved in deionized water at 56: 95: 5 and to mix the back adding above-mentioned oven dry powder and stirring 30min.To be that 0.7 citric acid is dissolved in and forms solution in the deionized water, and slowly add in the above-mentioned suspension-turbid liquid that 80 ℃ of continuous stir about 2h form behind the spawns at 70 ℃ of dry 24h down with the metal ion mol ratio.Rise to after 850 ℃ with 5 ℃/min and in the atmosphere that contains oxygen 30%, to calcine 12h, obtain the end-product doping type lithium manganate after the cooling naturally.Adopt Rigaku-D/MAX-2550PC type X-ray diffractometer (Cu target K beam wavelength is 0.154nm) with 0.02 °/s rate test sample crystal X ray diffracting spectrum.
Above-mentioned product LiMn2O4, acetylene black, Kynoar (PVdF) are that mixing in 85: 10: 5 adds a certain amount of n-formyl sarcolysine base pyrrolidones (NMP) stirring formation slurry by mass ratio, be coated on the aluminium foil, oven dry, cut-parts, compressing tablet, make anodal back with the lithium sheet as negative pole, with LiPF 6Concentration be the ethyl carbonate of 1.0mol/L and methyl carbonate (volume ratio is 1: 1) organic solution as electrolyte, polypropylene microporous film is assembled into 2032 button cells as barrier film.Carrying out charge-discharge test between 3.0V to 4.3V with the 110mA/g electric current.
Embodiment 2:
2.0mol/L manganese sulfate MnSO 44H 2The CoSO of O and 0.2mol/L 47H 2O mixed aqueous solution, concentration are the sodium hydrate aqueous solution of 4.5mol/L and the Li that 1kg has spinel structure and well-crystallized 3.8Cu 0.2Mn 4.5O 10.5F 0.5Pressed powder joins in the reactor evenly, continuously and react simultaneously, control pH value is 9.2, and the aqueous solution in the simultaneously continuous stirred autoclave obtains the solid-liquid mixtures material after reaction finishes, filter afterwards, washing, drying operation, obtain powder stock.With its oxygen content be in 30% the atmosphere prior to 500 ℃ of reaction 12h, and then, obtain end-product doping type lithium manganate pressed powder in 820 ℃ of calcining 24h.Carrying out X-ray diffraction by described mode described in the embodiment 1 tests and makes 2032 button cells and carry out charge-discharge test.
Embodiment 3:
Weighing 607.6g electrolysis MnO 2, 1020.4g have spinel structure and well-crystallized through the Li behind the acid etching 10min among the embodiment 1 3.8Cu 0.2Mn 4.5O 11Pressed powder, 15.6g LITHIUM BATTERY Li 2CO 3, 74.4g nanometer Li 2MoO 4After four kinds of powder mix, add in the ball grinder with the 500ml absolute ethyl alcohol, the mass ratio of Φ 10 stainless steel balls and above-mentioned raw materials is 0.55, and planetary ball mill rotating speed 150r/min carries out ball milling 1h.Mixture behind the above-mentioned ball milling is risen to 850 ℃ of calcining 5h with 1 ℃/min after oxygen content is that 5 ℃/min rises to 500 ℃ in 30% the atmosphere, obtains 1.5kg end-product doping type lithium manganate pressed powder.Carrying out X-ray diffraction by described mode described in the embodiment 1 tests and makes 2032 button cells and carry out charge-discharge test.
Comparative example 1:
Weighing 274.8gLiOHH 2O, 1028.3g electrolysis MnO 2, 147.1g cobalt acetate Co (CH 3COO) 24H 2After three kinds of powder of O mix, add in the ball grinder with the 450ml absolute ethyl alcohol, the mass ratio of Φ 10 stainless steel balls and above-mentioned raw materials is 0.55, and planetary ball mill rotating speed 100r/min carries out ball milling 1h.Pre-burning 8h after 5 ℃/min of mixture behind the above-mentioned ball milling risen to 500 ℃, add in the ball grinder with the 300ml absolute ethyl alcohol after naturally cooling to room temperature then, the mass ratio of Φ 10 stainless steel balls and above-mentioned raw materials is 1.0, planetary ball mill rotating speed 100r/min, carry out behind the ball milling 1h sintering 12h after oxygen content is that 5 ℃/min rises to 850 ℃ in 30% the atmosphere, obtain the about 1.0kg comparative sample of end-product after reducing to room temperature naturally.Carrying out X-ray diffraction by mode described in the embodiment 1 tests and makes 2032 button cells and carry out charge-discharge test.By the comparison to XRD spectra, the crystallinity of the sample in the foregoing description 1～3 all is better than comparative example 1 sample, and is spinel structure, does not find impurity peaks except that comparative example 1.
The normal temperature of table 1 embodiment and comparative example and high-temperature behavior are relatively
Figure BSA00000479333500071

Claims (10)

1. the induced crystallization synthetic method of a lithium ion secondary battery anode dusty material is characterized in that may further comprise the steps:
(1) compares n by metal pantogen Li: (n Mn+ n M)=0.40～0.75 with lithium-containing compound, contain manganese compound, contain compound or fusing point one or more raw materials as crystal growth in the solid matter below 860 ℃ of doped chemical, adds pressed powder as crystalline matrix; The main body that is characterized as of described pressed powder has Li 1+xMn 2-y-zM zO 3-δThe composition general formula, wherein M is a doped chemical ,-1≤x≤1;-1≤y≤2; Y-x≤1; 0≤z≤0.75;-0.5≤δ≤0.5, δ is determined to keep electric neutrality by the valence state of metal ion;
(2) above-mentioned substance is evenly mixed or combination, obtain powder stock;
(3) in oxygen-containing atmosphere, after calcining at least once under 600～1100 ℃ the high temperature, obtaining end-product is that main body is the lithium ion secondary battery anode dusty material of spinel structure.
2. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 1, it is characterized in that lithium-containing compound is LiBO in the described step (1) 22H 2O, LiOHH 2O, Li 2CO 3, LiHCO 3, Li 2B 4O 75H 2O, Li 2SO 4H 2O, Li 2SiO 3, LiClH 2O, LiF, LiBrH 2O, LiNO 3, at least a in lithium formate, lithium acetate, lithium oxalate, ethanedioic acid hydrogen lithium, lithium salicylate, lithium tartrate, acid lithium tartrate or the lithium citrate;
Containing manganese compound in the described step (1) is MnOOH, Mn (OH) 2, MnO 2, MnCO 3, Mn 2O 3, Mn 3O 4, MnCl 24H 2O, MnF 2, MnBr 24H 2O, MnI 24H 2O, Mn (NO 3) 26H 2O, MnSO 44H 2At least a in O, manganese oxalate, formic acid manganese, manganese acetate or the manganese citrate;
Doped chemical in the described step (1) is at least a among Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Mo, W, Ni, Cu, Zn, Ba, Bi, Zr, Y, Sr, Ru, Rh, Pd, Cd, In, Sn, Sb, Ag, Pb, Ta, Hf, Re, Os, Ir, the Au;
Fusing point is H at the solid matter below 860 ℃ in the described step (1) 3BO 3, B 2O 3, Li 2MoO 4, Li 2WO 4, Bi 2O 3In at least a.
3. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 1, it is characterized in that the compound that contains doped chemical in the described step (1) is at least a in oxide, hydroxide, carbonate, subcarbonate, halide, sulphite, nitrate, oxalates, formates, acetate, salicylate or the citrate.
4. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 1, it is characterized in that being characterized as of the middle pressed powder of described step (1): main body belongs to MnO-Li in the Li-Mn-O ternary phase diagrams 2MnO 3-MnO 2In-MnO the zone; Agent structure belongs to cube, at least a in four directions or the rhombic system; The middle particle diameter (D50) of pressed powder is 0.1～15 μ m.
5. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 1, it is characterized in that at least a processing that pressed powder injects or breaks up through surperficial coating, surface micro etching, ion in the described step (1); Described surface micro etching is the low concentration acid corrosion that has added additive; Described ion is injected under certain condition at least a in F, P, Cl, Si, S or the Se element has been mixed at least one class position of crystalline matrix in the above-mentioned three class positions of Mn lattice position, O lattice position, Mn lattice position and O lattice position.
6. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 1, it is characterized in that evenly mixing in the described step (2) or combination is at least a in co-precipitation, pasty material parcel, ball milling, stirring, the concussion;
Described co-precipitation forms suspension solution for material in the step (1) is added in the entry, add alkaline aqueous solution control pH value and be 7.5～12.5 and carry out precipitation reaction, obtains the solid-liquid mixtures material, filters afterwards, washing, drying operation, obtains powder stock;
Described pasty material parcel forms suspension solution for material in the step (1) is added in the entry, behind the adding complexing agent aqueous solution, carry out drying 2～48h after 30～100 ℃ of continuous 1～24h of stirring form spawn, obtains powder stock;
Described ball-milling method is that material in the step (1) is added ball-milling additive, carries out drying behind ball milling 1～48h, obtains powder stock;
Described paddling process forms suspension solution for material in the step (1) is added in the entry, constantly being stirred to water at 80～100 ℃ evaporates fully, obtains powder stock.
7. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 1, it is characterized in that evenly mixing in the described step (2) or in conjunction with the mutual spatial relationship of back material be granule center on bulky grain, bulky grain around granule, granule around bulky grain and bulky grain be that the growth of matrix covers around short grained intermediate state or with pressed powder as crystalline matrix.
8. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 1, it is characterized in that end-product in the described step (3) is that main body is that the lithium ion secondary battery anode dusty material of spinel structure is LiMn 2O 4Or its modified product.
9. the induced crystallization synthetic method of described according to Claim 8 a kind of lithium ion secondary battery anode dusty material, it is characterized in that described modification comprise the surface coat, bulk phase-doped, the surface coats and bulk phase-doped above-mentioned three kinds of modification mode at least a.
10. according to the induced crystallization synthetic method of the described a kind of lithium ion secondary battery anode dusty material of claim 9, it is characterized in that mixing described bulk phase-doped comprising at high proportion, have LiMn 1.4Cr 0.2Ni 0.4O 4, LiMnCoO 4And other similar substance all is regarded as LiMn 2O 4Doped derivatives at high proportion.
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