CN105024059A - Multi-component composite lithium battery positive electrode material, preparing method of multi-component composite lithium battery positive electrode material and high-energy lithium battery - Google Patents

Multi-component composite lithium battery positive electrode material, preparing method of multi-component composite lithium battery positive electrode material and high-energy lithium battery Download PDF

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Publication number
CN105024059A
CN105024059A CN201410173137.7A CN201410173137A CN105024059A CN 105024059 A CN105024059 A CN 105024059A CN 201410173137 A CN201410173137 A CN 201410173137A CN 105024059 A CN105024059 A CN 105024059A
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lithium battery
positive electrode
battery positive
electrode material
component composite
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郭成
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Taoyuan Sanhe Energy Technology Co Ltd
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Taoyuan Sanhe Energy Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a multi-component composite lithium battery positive electrode material, a preparing method of the multi-component composite lithium battery positive electrode material and a high-energy lithium battery. The multi-component composite lithium battery positive electrode material has a general formula of Li<1+n>V<1-x-y-z>Cr<x>Nb<y>Mo<z>O8, wherein in the formula, the Li represents lithium, the V represents vanadium, the Cr represents chromium, the Nb represents niobium, the Mo represents molybdenum, the O represents oxygen, the N is -0.1 to 1.15, and the x equals to the y, equals to the z and is 0.25 to 0.75. The preparing method of the multi-component composite lithium battery positive electrode material has the advantages that NH4VO3, (NH4)3NbO(C204)3] 4H20, (NH4)2Cr207 and (NH4)6Mo7024 4H20 are added according to the proportion; heating high-temperature fusion is carried out; then, the materials are quickly cooled in the deionized water to form V2O5, Nb2O5, Cr2O3 and Mo2O3 mixed sol; LiOH is added into the mixed sol and is sufficiently mixed; spray drying is carried out to obtain the Li<1+n>V<1-x-y-z>Cr<x>Nb<y>Mo<z>O8 powder; then, heat treatment is carried out, and the Li<1+n>V<1-x-y-z>Cr<x>Nb<y>Mo<z>O8 is obtained. The multi-component composite lithium battery positive electrode material has the advantages that the grain diameter is small; the electrolyte seepage is facilitated; under the conditions of high-magnification discharging and charging, the material utilization rate and the specific capacity are higher. The discharging is performed under the 200mA/g of current density. The electrode synthesized by the materials simultaneously has higher discharging capacity and higher circulation stability.

Description

A kind of multi-component compound lithium battery positive electrode and preparation method thereof and high power lithium battery
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of multi-component compound lithium battery positive electrode and preparation method thereof and high power lithium battery.
Background technology
Along with the quick consumption of non-renewable energy resources and going from bad to worse of biological environment, before the new clean energy resource that can support economy and social sustainable development occurs, we can only make an effort in the service efficiency improving constantly energy, therefore, more and more higher requirement will be proposed to the storage of energy and release.Portable, clean, high-energy-density and particularly powerful energy supplyystem more and more receive publicity.Traditional lithium-ion battery, because its energy density high, flexible design, good cycling stability, life-span length, environmental friendliness etc., is most widely used in mobile electronic device.But the application being applied in as electrical source of power in the vehicles such as powerful automobile, in high-power, high-energy-density device, traditional lithium-ion battery is all subject to the impact of a crucial conditionality factor, and namely the specific capacity of cell positive material is obviously on the low side.
The operating voltage of battery depends mainly on the positive electrode of high potential, and the capacity of negative material generally will far above positive electrode simultaneously.Therefore, the battery material with comparatively high working voltage (V) and Large Copacity (C) becomes two Main way of Study on Li-ion batteries.Owing to (being about 4.6V by the highest safe voltage of organic solvent electrolyte system extensively adopted up till now, vs Li/Li+) restriction, the space of being improved energy storage and release efficiency by the mode improving battery operating voltage is further very limited, before this restriction does not break through, the raising of anode material for lithium-ion batteries capacity become at present and in the future one period Study on Li-ion batteries major fields and breach.
Manganese base and vanadium base anode material are the two large systems paid close attention at present.Manganese-based anode material, as mixed the LiNi0.5Mn1.504 that Ni is formed, the voltage platform that its Li+ ion embeds matrix reaches 4.8V, be the good example of exploitation high voltage platform, but this based material capacity is obviously on the low side, only has 140mAh/g (C/7).Vanadium base anode material, as V 2o 5and LiV 3o 8deng barium oxide, during embedding lithium, its V5+ chemical valence reduces to+3.5 (ω Li3V205) and+3.67 (Li5V308) respectively, and according to theoretical specific capacity computing formula: Cm=26800n/M, (n is the number of Li+ ion; M is relative molecular mass), they can obtain the theoretical specific capacity of 442 and 372mAh/g respectively, when 3 Li+ ions are deviate from from Li3V2 (PO4) 3, also 197mAh/g can be discharged, this specific capacity is the highest in phosphate system at present, has become positive electrode of new generation at present.
Summary of the invention
For the above-mentioned problems in the prior art, a kind of multi-component compound lithium battery positive electrode and preparation method thereof and high power lithium battery are provided, by material structure Composite, shorten the diffusion length of Li+ ion, improve charge transport efficiency, increase simultaneously and embed multiple Li+ ion gap, impel the change that multiple valence state occurs, improve battery capacity.
The technical scheme that the present invention takes is: a kind of multi-component compound lithium battery positive electrode, and the general formula of described positive electrode material of multi-component composite lithium ion cell is Li 1+nv 1-x-y-zcr xnb ymo zo 8, in formula, Li represents lithium, and V represents vanadium, Cr Biao Shi Chrome, and Nb represents niobium, and Mo represents molybdenum, and 0 represents oxygen, N=-0.1-1.15, x=y=z=0.25-0.75.
The method of described positive electrode multiple elements design comprises the steps: that (1) is by NH4VO3, (NH4) 3NbO (C204) 3] 4H20, (NH4) 2Cr207; (NH4) 6Mo70244H20 raw material NH4VO3:(NH4 in molar ratio) 3NbO (C204) 3] 4H20:(NH4) 2Cr207:(NH4) fully to mix at 6Mo70244H20=1: 1: 1: 1; (2) by mixing cpd 450-900 DEG C of melting in Muffle furnace, after constant temperature 3-5 hour, be cooled to normal temperature rapidly, within after adding ionized water vigorous stirring 1-3 hour, obtain the gluey slurry of mixing; (3) joined by LiOH solution in the gluey slurry of mixing, the mol ratio of LiOH and mixing cpd is 1.05: 3, continues to stir 1-3 hour; (4) gluey for gained slurry spraying dry is obtained Li 1+nv 1-x-y-zcr xnb ymo zo 8powder, then spraying gained powder is dried and obtained Li 1+nv 1-x-y-zcr xnb ymo zo 8.
Invention also improves a kind of high-energy lithium battery tankage and comprehensive electrochemical properties, comprise positive pole, negative pole and organic solvent electrolyte, its positive pole contains above-mentioned Li 1+nv 1-x-y-zcr xnb ymo zo 8multi-element composite material.
The technology that the present invention takes and the most basic difference of conventional method are: conventional method does leading with a kind of material, and other elements supplement the deficiency of leading material as doped chemical, and the present invention adopts balanced equity to combine.
The present invention adopts compound to prepare lithium vanadium, lithium niobium, lithium chromium, lithium molybdenum compound presoma, thermal decomposition in water afterwards, is prepared into the uniform Li of pattern by atomization 1+nv 1-x-y-zcr xnb ymo zo 8multi-element composite material, this material diameter is 9-12um, and this structure is conducive to the infiltration of electrolyte, simultaneously because particle size diameter is 9-12unm, substantially reduces the distance of process needed for Li+ ion diffuse.Therefore, under high-multiplying power discharge and charge condition, utilance and the specific capacity of material are higher.Discharge under the current density of 200mA/g, the Li of this materials synthesis 1+nv 1-x-y-zcr xnb ymo zo 8electrode has very high discharge capacity and good cyclical stability simultaneously.Under 300mA/g, electric discharge can obtain the ratio discharge capacity of 330mAh/g, and the capacitance loss of single cycle is only 0.20%.Under more high current density 1A/g after circulation 200 times, it still can reach 288mAh/g than discharge capacity, and stable circulation performance significantly improves.Li of the present invention 1+nv 1-n-y-zcr xnb ymo zo 8composite lithium battery can meet electric tool, electrical source of power and in the vehicles such as powerful automobile application completely.
Accompanying drawing explanation
Fig. 1 is specific discharge capacity and the discharging efficiency comparison diagram of multi-component compound lithium battery positive electrode of the present invention;
Fig. 2 is the higher efficiency curve chart of multi-component compound lithium battery positive electrode of the present invention.
Embodiment
The invention provides a kind of multi-component compound lithium battery positive electrode, its general formula is Li 1+nv 1-x-y-zcr xnb ymo zo 8, in formula, Li represents lithium, and V represents vanadium, Cr Biao Shi Chrome, and Nb represents niobium, and Mo represents molybdenum, and 0 represents oxygen, N=-0.1-1.15, x=y=z=0.25-0.75.
Multi-component compound lithium battery method for preparing anode material example 1 of the present invention:
1,350.94g NH is first weighed 4vO 3; 499.06g (NH 4) 3nbO (C 2o 4) 3] 4H 2o; 756.21g (NH 4) 2cr 2o 7; 3707.88g (NH 4) 6mo 7o 244H 2o fully mixes in ball grinder, and Ball-milling Time is 1-3 hour.
2, by mixing cpd 800 DEG C of meltings in JNL Muffle furnace, constant temperature, after 2 hours, is cooler than normal temperature rapidly, and after adding ionized water, vigorous stirring obtains the gluey slurry of mixing for 1.5 hours.
3, joined by LiOH solution in the gluey slurry of mixing, the mol ratio of lithium and mixing cpd is 1.0-1.05: 2.95-3.05, continues to stir 1-3 hour.
4, by dry with pneumatic spray drying device for gluey for gained slurry, adopt and fluidized drying method, atomization plant adopts double-current method nozzle, vibration-type charging, charging rate is 50ml/min, and atomization air pressure is 0.2Mpa, and air inlet temperature is 400 DEG C, outlet temperature is 130 DEG C, and exit flow is separated emptying through one-level whirlpool.Spraying gained object constant temperature drying at 120 DEG C, carries out ball milling 1-3 hour after oven dry.
Sample this 100g routinely lithium electricity formula be made into positive plate and be assembled into 1865 type batteries with conventional anode and record the first specific capacity of sample and be: 335mAh/g, circulate after 200 times, it still can reach 288mAh/g than discharge capacity, and stable circulation performance is good.
Multi-component compound lithium battery method for preparing anode material of the present invention:
1, first 701.88gNH is weighed 4vO 3; 998.12g (NH 4) 3nbO (C 2o 4) 3] 4H 2o; 1512.42g (NH 4) 2cr 2o 7; 7415.76g (NH 4) 6mo 7o 244H 2o, fully mixes in ball grinder, and Ball-milling Time is 1-3 hour.
2, by mixing cpd 900 DEG C of meltings in JNL Muffle furnace, constant temperature, after 2 hours, is cooler than normal temperature rapidly, and after adding ionized water, vigorous stirring obtains the gluey slurry of mixing for 1 hour.
3, joined by LiOH solution in the gluey slurry of mixing, the mol ratio of lithium and mixing cpd is 1.05: 3, continues to stir 1-3 hour.
4, by dry with pneumatic spray drying device for gluey for gained slurry, adopt and fluidized drying method, atomization plant adopts double-current method nozzle, vibration-type charging, charging rate is 50m1/min, and atomization air pressure is 0.2Mpa, and air inlet temperature is 400 DEG C, outlet temperature is 150 DEG C, and exit flow is separated emptying through one-level whirlpool.Spraying gained object after constant temperature drying, carries out ball milling 1-3 hour after oven dry at 120 DEG C.
Sample this 100g routinely lithium electricity formula be made into positive plate and be assembled into 1865 type batteries with conventional anode and record the first specific capacity of sample and be: 330mAh/g, circulate after 200 times, it still can reach 280mAh/g than discharge capacity, and stable circulation performance is good.

Claims (3)

1. a multi-component compound lithium battery positive electrode, is characterized in that: the general formula of described positive electrode material of multi-component composite lithium ion cell is Li 1+nv 1-x-y-zcr xnb ymo zo 8, in formula, Li represents lithium, and V represents vanadium, and Cr Biao Shi Chrome, Nb represents niobium, and Mo represents molybdenum, and O represents oxygen, N=-0.1-1.15, x=y=z=0.25-0.75.
2. the preparation method of a kind of multi-component compound lithium battery positive electrode as claimed in claim 1, is characterized in that: comprise the steps: that (1) is by NH4VO3, (NH4) 3NbO (C204) 3] 4H20, (NH4) 2Cr207; (NH4) 6Mo70244H20 raw material NH4VO3:(NH4 in molar ratio) 3NbO (C204) 3] 4H20:(NH4) 2Cr207:(NH4) fully to mix at 6Mo70244H20=1: 1: 1: 1; (2) by mixing cpd 450-900 DEG C of melting in Muffle furnace, after constant temperature 3-5 hour, be cooled to normal temperature rapidly, within after adding ionized water vigorous stirring 1-3 hour, obtain the gluey slurry of mixing; (3) joined by LiOH solution in the gluey slurry of mixing, the mol ratio of lithium and mixing cpd is 1-1.05: 3-3.05, continues to stir 1-3 hour; (4) gluey for gained slurry spraying dry is obtained Li 1+nv 1-x-y-zcr xnb ymo zo 8powder, then spraying gained powder is dried and obtained Li 1+nv 1-x-y-zcr xnb ymo zo 8.
3. a high power lithium battery, comprises positive pole, negative pole and organic solvent electrolyte, it is characterized in that: described positive pole comprises multi-component compound lithium battery positive electrode according to claim 1.
CN201410173137.7A 2014-04-28 2014-04-28 Multi-component composite lithium battery positive electrode material, preparing method of multi-component composite lithium battery positive electrode material and high-energy lithium battery Pending CN105024059A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11444278B2 (en) 2017-11-24 2022-09-13 Lg Energy Solution, Ltd. Cathode material for lithium secondary battery, and preparation method therefor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11444278B2 (en) 2017-11-24 2022-09-13 Lg Energy Solution, Ltd. Cathode material for lithium secondary battery, and preparation method therefor

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Application publication date: 20151104