CN102208611B - A kind of induced crystallization synthetic method of lithium ion secondary battery positive electrode dusty material - Google Patents

A kind of induced crystallization synthetic method of lithium ion secondary battery positive electrode dusty material Download PDF

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CN102208611B
CN102208611B CN201110101638.0A CN201110101638A CN102208611B CN 102208611 B CN102208611 B CN 102208611B CN 201110101638 A CN201110101638 A CN 201110101638A CN 102208611 B CN102208611 B CN 102208611B
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lithium ion
lithium
secondary battery
ion secondary
dusty material
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CN102208611A (en
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王明月
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    • Y02E60/10—Energy storage using batteries

Abstract

A kind of induced crystallization synthetic method of lithium ion secondary battery positive electrode dusty material, it is characterized by the feed, add pressed powder as crystalline matrix, above-mentioned substance is mixed, then calcine at least one times under the high temperature of 600 ~ 1100 DEG C in oxygen-containing atmosphere, obtain the lithium ion secondary battery anode dusty material that end-product and main body are spinel structure.Superiority of the present invention is: the method can improve product crystallization property and implant uniformity, the spinel structure positive electrode with features such as rule of surface, compacted density are high, impurity content is low to raising performance of lithium ion battery, promote lithium ion battery and apply more widely there is important economic implications and practical value.

Description

A kind of induced crystallization synthetic method of lithium ion secondary battery positive electrode dusty material
(1) technical field:
The invention belongs to novel energy resource material technology field, for lithium rechargeable battery provides a kind of positive powder powder material with high cyclical stability and excellent high temperature cycle performance.
(2) background technology:
Lithium rechargeable battery is since the nineties in last century is invented by Japanese Sony Corporation, because have that operating voltage is high, energy density be large, have extended cycle life, memory-less effect, the series of advantages such as environmental protection, so obtain develop rapidly at portable electric appts as fields such as cordless telephone, notebook computer, music player, digital cameras, become the Main way of secondary cell development.Energy crisis and environmental pollution make to find clean, reproducible secondary energy sources to be become and realizes human social task urgently to be resolved hurrily; Simultaneously due to the above-mentioned advantage of lithium rechargeable battery, as a kind of energy accumulating device, its application constantly expands and keeps the large-scale development.The existing application also development in fields such as electric bicycle, battery-operated motor cycle, electric tool, hybrid electric vehicle, pure electric vehicle, energy storage at present.
Positive electrode is one of the main member of lithium rechargeable battery and the key determinant of performance quality.Current 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.The positive electrode of its sandwich has that fail safe is poor, high in cost of production shortcoming; There is the shortcomings such as conductivity is low, high rate performance is poor 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 excellent, security performance is good, advantages of environment protection, is one of the material of lithium ion battery of future generation particularly power lithium ion battery most prospect.
The LiMn of current 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 Homogeneous phase mixing of metallic element on atomic level, there is the advantages such as synthesis temperature is low, pattern is excellent, chemical property is good, but also there is a series of shortcomings such as synthesis technique complexity, cost is high, product compacted density is low, suitability for industrialized production is difficult.And manganese compound and lithium compound generally form to fire in the temperature range of 700 ~ 850 DEG C after special ratios mixing by high temperature solid-state method because production operation simple, be easy to the first-selected production method that suitability for industrialized production etc. becomes spinels positive electrode.But the material that above-mentioned conventional high-temperature solid phase method is produced generally has following deficiency, namely product crystallinity poor, adulterate uneven, crystal surface pattern is irregular, compacted density is low, impurity content is high, and then cause as the dissolving of the metallic elements such as Mn, electrolyte decompose under high potential, a stable condition time there is the instability etc. of Jahn-Teller effect, material lattice, again so cause that product specific capacity is low, cycle life is shorter (cycle life especially during high temperature), be made into battery after a series of shortcomings such as energy density is low.
(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, synthesis has the positive electrode of the spinel structure of the features such as rule of surface, compacted density is high, impurity content is low, to raising performance of lithium ion battery, promotes lithium ion battery and applies more widely and have important economic implications and practical value.
An induced crystallization synthetic method for lithium ion secondary battery anode dusty material, is characterized in that comprising the following steps:
(1) n is compared by metal Elements Atom li: (n mn+ n m)=0.40 ~ 0.75, using lithium-containing compound, containing manganese compound, containing one or more raw materials as crystal growth in the compound of doped chemical or the solid matter of fusing point below 860 DEG C, adds pressed powder as crystalline matrix; The feature of described pressed powder is that main body has Li 1+xmn 2-y-zm zo 3-δcomposition general formula, wherein M is 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 carried out Homogeneous phase mixing or combination, obtain powder stock;
(3) in oxygen-containing atmosphere, to calcine at least one times under the high temperature of 600 ~ 1100 DEG C, the lithium ion secondary battery anode dusty material that end-product and main body are spinel structure is obtained.
In step described above (1), lithium-containing compound is LiBO 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, lithium formate, lithium acetate, lithium oxalate, ethanedioic acid hydrogen lithium, lithium salicylate, lithium tartrate, acid tartrate acid lithium or lithium citrate at least one.
Containing manganese compound in step described above (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 one in O, manganese oxalate, formic acid manganese, manganese acetate or manganese citrate.
Doped chemical in step described above (1) is at least one in 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, Au.
Doped chemical in step described above (1) is at least one in Al, Ti, Cr, Co, Mo or Ni.
The compound containing doped chemical in step described above (1) is at least one in oxide, hydroxide, carbonate, subcarbonate, halide, sulphite, nitrate, oxalates, formates, acetate, salicylate or citrate.
In step described above (1), the solid matter of fusing point below 860 DEG C is H 3bO 3, B 2o 3, Li 2moO 4, Li 2wO 4, Bi 2o 3middle at least one.
In step described above (1), the feature of pressed powder is: main body belongs to MnO-Li in Li-Mn-O ternary phase diagrams 2mnO 3-MnO 2in-MnO region.
In step described above (1), the feature of pressed powder is: main body belongs to MnO-Li in Li-Mn-O ternary phase diagrams 2mnO 3-MnO 2iII, IV region in-MnO region.
In step described above (1), the feature of pressed powder is: main body belongs to MnO-Li in Li-Mn-O ternary phase diagrams 2mnO 3-MnO 2iV region in-MnO region.
The feature of pressed powder is in step described above (1): agent structure belongs to cube, at least one in four directions or rhombic system.
In step described above (1), the feature of pressed powder is: agent structure is the cubic system with product with same structure.
In step described above (1), the middle particle diameter (D50) of pressed powder is 0.1 ~ 15 μm.
In step described above (1), the middle particle diameter (D50) of pressed powder is desired end product 0.3 ~ 0.8 times.
In step described above (1), pressed powder is through Surface coating, surface micro etching, ion implantation or at least one process in breaing up.
Surface micro etching described above is the low concentration acid corrosion adding additive.
Ion implantation described above is at least one be mixed with 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 under certain condition in F, P, Cl, Si, S or Se element.
In step described above (2), Homogeneous phase mixing or combination are at least one in co-precipitation, pasty material parcel, ball milling, stirring, concussion.
Co-precipitation described above is for being added to the water formation suspension solution by material in step (1), adding alkaline aqueous solution control ph is 7.5 ~ 12.5 carry out precipitation reaction, obtain solid-liquid mixtures material, carry out afterwards filtering, wash, drying operation, obtain powder stock.
Pasty material parcel described above, for material in step (1) is added to the water formation suspension solution, after adding complexing agent aqueous solution, constantly stirs after 1 ~ 24h forms spawn at 30 ~ 100 DEG C and carries out drying 2 ~ 48h, obtain powder stock.
Ball-milling method described above, for material in step (1) is added ball-milling additive, carries out ball milling 1 ~ 48h post-drying, obtains powder stock.
Paddling process described above is for being added to the water formation suspension solution by material in step (1), and being constantly stirred to water at 80 ~ 100 DEG C evaporates completely, obtains powder stock.
In step described above (2), the mutual spatial relationship of Homogeneous phase mixing or the rear material of combination is that granule covers around bulky grain and bulky grain around short grained intermediate state or using the growth that the pressed powder as crystalline matrix is matrix around bulky grain, bulky grain around granule, granule.
In step described above (2), the mutual spatial relationship of Homogeneous phase mixing or the rear material of combination is that granule covers around bulky grain or using the growth that the pressed powder as crystalline matrix is matrix.
In step described above (2), the mutual spatial relationship of Homogeneous phase mixing or the rear material of combination is that the growth being matrix using the pressed powder as crystalline matrix covers.
End-product in step described above (3) and main body are the lithium ion secondary battery anode dusty material of spinel structure is LiMn 2o 4or its modified product.
Modification described above comprises at least one in Surface coating, bulk phase-doped, Surface coating and bulk phase-doped above-mentioned three kinds of modification mode.
Bulk phase-doped comprising described above adulterates at high proportion, has LiMn 1.4cr 0.2ni 0.4o 4, LiMnCoO 4and other similar substance is all regarded as LiMn 2o 4doped derivatives at high proportion.
Superiority of the present invention is: the product synthesized according to production process of the present invention can improve product crystallization property and implant uniformity, there is the features such as rule of surface, compacted density is high, impurity content is low, to raising performance of lithium ion battery, promote lithium ion battery and apply more widely there is important economic implications and practical value.
(4) accompanying drawing illustrates:
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) region is LiMn 3o 4-Mn 3o 4-MnO-LiMn 3o 4the part comprised, (II) region 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 comprised, (III) region is LiMn 2o 4-Mn 3o 4-MnO 2-LiMn 2o 4the part comprised, (IV) region is LiMn 2o 4-Li 6.5mn 5o 12-Li 4mn 5o 12-MnO 2-LiMn 2o 4the part comprised, above-mentioned four regions exist overlapping at boundary;
Fig. 2 is that the X-ray diffraction spectrogram of synthetic sample in execution mode compares;
Fig. 3 is that the discharge curve of synthetic sample in execution mode compares;
Fig. 4 is that the cyclic curve of synthetic sample in execution mode compares.
(5) embodiment:
Embodiment 1:
The main body being 5.1 μm by particle diameter in 550g (D50) 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, spends deionized water three times, dries 12h for 120 DEG C.By lithium acetate Li (CH 3cOO) 2H 2o, manganese acetate Mn (CH 3cOO) 24H 2o, cobalt acetate Co (CH 3cOO) 24H 2o is be dissolved in deionized water and mix after add above-mentioned oven dry powder stir 30min at 56: 95: 5 by Li: Mn: Co mol ratio.Form solution in deionized water by dissolving with the metal ion mol ratio citric acid that is 0.7, and slowly add in above-mentioned suspension-turbid liquid, 80 DEG C of continuous stir about 2h to form after spawns dry 24h at 70 DEG C.In containing the atmosphere of oxygen 30%, calcine 12h after rising to 850 DEG C with 5 DEG C/min, after Temperature fall, obtain end-product doping type lithium manganate.Adopt Rigaku-D/MAX-2550PC type X-ray diffractometer (Cu target K beam wavelength is 0.154nm) with 0.02 °/s rate test Sample crystals X ray diffracting spectrum.
Above-mentioned product LiMn2O4, acetylene black, Kynoar (PVdF) are that 85: 10: 5 mixing add a certain amount of nitrogen methyl pyrrolidone (NMP) stirring formation slurry in mass ratio, be coated on aluminium foil, oven dry, cut-parts, compressing tablet, using lithium sheet as negative pole after obtained positive 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, as barrier film, is assembled into 2032 button cells.Between 3.0V to 4.3V, charge-discharge test is carried out with 110mA/g electric current.
Embodiment 2:
The manganese sulfate MnSO of 2.0mol/L 44H 2the CoSO of O and 0.2mol/L 47H 2o mixed aqueous solution, concentration are that the sodium hydrate aqueous solution of 4.5mol/L and 1kg have spinel structure and the Li of well-crystallized 3.8cu 0.2mn 4.5o 10.5f 0.5pressed powder joins in reactor evenly, continuously simultaneously and reacts, control ph is 9.2, and the aqueous solution simultaneously in continuous stirred autoclave, obtains solid-liquid mixtures material after reaction terminates, carry out afterwards filtering, wash, drying operation, obtain powder stock.Be prior to 500 DEG C of reaction 12h in the atmosphere of 30% in oxygen content by it, and then in 820 DEG C of calcining 24h, obtain end-product doping type lithium manganate pressed powder.Carry out X-ray diffraction test by described mode described in embodiment 1 and make 2032 button cells and carry out charge-discharge test.
Embodiment 3:
Weigh 607.6g electrolysis MnO 2, 1020.4g has spinel structure and the Li after the acid etching 10min in embodiment 1 of well-crystallized 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 ball grinder together with 500ml absolute ethyl alcohol, the mass ratio of Φ 10 stainless steel ball and above-mentioned raw materials is 0.55, and planetary ball mill rotating speed 150r/min, carries out ball milling 1h.Be rise to 850 DEG C of calcining 5h with 1 DEG C/min after 5 DEG C/min rises to 500 DEG C in the atmosphere of 30% in oxygen content by the mixture after above-mentioned ball milling, obtain 1.5kg end-product doping type lithium manganate pressed powder.Carry out X-ray diffraction test by described mode described in embodiment 1 and make 2032 button cells and carry out charge-discharge test.
Comparative example 1:
Weigh 274.8gLiOHH 2o, 1028.3g electrolysis MnO 2, 147.1g cobalt acetate Co (CH 3cOO) 24H 2after O tri-kinds of powder mix, add in ball grinder together with 450ml absolute ethyl alcohol, the mass ratio of Φ 10 stainless steel ball 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 mixture 5 DEG C/min after above-mentioned ball milling is risen to 500 DEG C, then add in ball grinder together with 300ml absolute ethyl alcohol after naturally cooling to room temperature, the mass ratio of Φ 10 stainless steel ball and above-mentioned raw materials is 1.0, planetary ball mill rotating speed 100r/min, be sinter 12h after 5 DEG C/min rises to 850 DEG C in the atmosphere of 30% in oxygen content after carrying out ball milling 1h, obtain end-product after being naturally down to room temperature and be about 1.0kg comparative sample.Carry out X-ray diffraction test by mode described in embodiment 1 and make 2032 button cells and carry out charge-discharge test.By the comparison to XRD spectra, the crystallinity of the sample in above-described embodiment 1 ~ 3 is all better than comparative example 1 sample, and is spinel structure, except comparative example 1, do not find impurity peaks.
Normal temperature and the high-temperature behavior of table 1 embodiment and comparative example compare

Claims (9)

1. an induced crystallization synthetic method for lithium ion secondary battery anode dusty material, is characterized in that comprising the following steps:
(1) n is compared by metal Elements Atom li: (n mn+ n m)=0.40 ~ 0.75, using lithium-containing compound, one or more raw materials as crystal growth containing manganese compound or fusing point in the solid matter below 860 DEG C, adds pressed powder as crystalline matrix; The feature of described pressed powder is that main body has Li 1+xmn 2-y-zm zo 3-δcomposition general formula, wherein M is 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 carried out Homogeneous phase mixing or combination, obtain powder stock;
(3) in oxygen-containing atmosphere, to calcine at least one times under the high temperature of 600 ~ 1100 DEG C, the lithium ion secondary battery anode dusty material that end-product and main body are spinel structure is obtained.
2. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 1, is characterized in that in described step (1), lithium-containing compound is LiBO 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, lithium formate, lithium acetate, lithium oxalate, ethanedioic acid hydrogen lithium, lithium salicylate, lithium tartrate, acid tartrate acid lithium or lithium citrate at least one;
Containing manganese compound in 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 one in O, manganese oxalate, formic acid manganese, manganese acetate or manganese citrate;
Doped chemical in described step (1) is at least one in 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, Au;
In described step (1), the solid matter of fusing point below 860 DEG C is H 3bO 3, B 2o 3, Li 2moO 4, Li 2wO 4, Bi 2o 3middle at least one.
3. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 1, is characterized in that the feature of pressed powder in described step (1) is: main body belongs to MnO-Li in Li-Mn-O ternary phase diagrams 2mnO 3-MnO 2in-MnO region; Agent structure belongs to cube, at least one in four directions or rhombic system; The middle particle diameter (D50) of pressed powder is 0.1 ~ 15 μm.
4. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 1, is characterized in that in described step (1), pressed powder is through Surface coating, surface micro etching, ion implantation or at least one process in breaing up; Described surface micro etching is the low concentration acid corrosion adding additive; Described ion implantation is at least one be mixed with the class position of crystalline matrix in Mn lattice position, O lattice position, Mn lattice position and O lattice position three class position under certain condition in F, P, Cl, Si, S or Se element.
5. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 1, is characterized in that in described step (2), Homogeneous phase mixing or combination are at least one in co-precipitation, pasty material parcel, ball milling, stirring, concussion;
Described co-precipitation is for being added to the water formation suspension solution by material in step (1), adding alkaline aqueous solution control ph is 7.5 ~ 12.5 carry out precipitation reaction, obtain solid-liquid mixtures material, carry out afterwards filtering, wash, drying operation, obtain powder stock;
Described pasty material parcel, for material in step (1) is added to the water formation suspension solution, after adding complexing agent aqueous solution, constantly stirs after 1 ~ 24h forms spawn at 30 ~ 100 DEG C and carries out drying 2 ~ 48h, obtain powder stock;
Described ball-milling method, for material in step (1) is added ball-milling additive, carries out ball milling 1 ~ 48h post-drying, obtains powder stock;
Described paddling process is for being added to the water formation suspension solution by material in step (1), and being constantly stirred to water at 80 ~ 100 DEG C evaporates completely, obtains powder stock.
6. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 1, to is characterized in that in described step (2) Homogeneous phase mixing or after combining, the mutual spatial relationship of material is that granule covers around bulky grain and bulky grain around short grained intermediate state or using the growth that the pressed powder as crystalline matrix is matrix around bulky grain, bulky grain around granule, granule.
7. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 1, is characterized in that end-product in described step (3) and main body be the lithium ion secondary battery anode dusty material of spinel structure are LiMn 2o 4or its modified product.
8. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 7, is characterized in that described modification comprises the one in Surface coating, bulk phase-doped, Surface coating and bulk phase-doped three kinds of modification mode.
9. the induced crystallization synthetic method of a kind of lithium ion secondary battery anode dusty material according to claim 8, is characterized in that describedly bulk phase-dopedly comprising LiMn 1.4cr 0.2ni 0.4o 4, LiMnCoO 4.
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