CN102694165A - High-capacity lithium-rich layered crystalline structured lithium battery cathode material and preparation thereof - Google Patents

High-capacity lithium-rich layered crystalline structured lithium battery cathode material and preparation thereof Download PDF

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CN102694165A
CN102694165A CN2012101890016A CN201210189001A CN102694165A CN 102694165 A CN102694165 A CN 102694165A CN 2012101890016 A CN2012101890016 A CN 2012101890016A CN 201210189001 A CN201210189001 A CN 201210189001A CN 102694165 A CN102694165 A CN 102694165A
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lithium
layered crystal
crystal structure
rich lithium
linbo
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张联齐
周恩娄
宋大卫
郭建
侯配玉
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Tianjin University of Technology
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Tianjin University of Technology
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Abstract

The invention discloses a high-capacity lithium-rich layered crystalline structured lithium battery cathode material, which is characterized in that a layer of LiNbO3 coats the particle surfaces of a powdery lithium-rich layered crystalline structured material, and the powdery lithium-rich layered crystalline structured material has a chemical formula xLi2MnO3.(1-x)LiNimConMn1-m-nO2, wherein x is more than or equal to 0.2 and less than or equal to 0.9, m is more than or equal to 0.1 and less than 1, and n is more than or equal to 0 and less than or equal to 0.5. A preparation method comprises the following steps of: first preparing a lithium-rich layered precursor, then preparing lithium-rich layered crystalline structured particles, and finally coating the particles by using the LiNbO3. The invention has the advantages that 1) the cathode material has high specific capacity, and the maximum specific capacity can reach 280mAh/g; 2) compared with an uncoated lithium-rich layered crystalline structured material, the lithium-rich layered crystalline structured material coated with the LiNbO3 has higher charge and discharge specific capacity and longer cycle life; and 3) the cathode material has high electrochemical performance under high voltage and high current density.

Description

Rich lithium layered crystal structure anode material of lithium battery of a kind of high power capacity and preparation thereof
Technical field
The present invention relates to the anode material for lithium-ion batteries technical field, rich lithium layered crystal structure anode material of lithium battery of particularly a kind of high power capacity and preparation thereof.
Background technology
Lithium battery has received extensive use in 3C Products such as mobile phone, digital camera, notebook computer since sony company commercialization first in 1991, in daily life, play an important role.Owing to have advantages such as high power density, high-energy-density, high cycle performance, lithium battery has also become the first-selected battery of the electric automobile of relatively generally acknowledging at present.Along with the continuous minimizing of international non-renewable energy resources reserves and the intensification day by day of environmental pollution, battery for electric automobile especially be that the research of lithium battery receives much concern.With regard to present circumstances; The research of anode material of lithium battery is compared with negative pole and is relatively lagged behind; No matter be in theory or in practical application, the capacity of the positive electrode that is adopted all is lower than negative material, and both required power density of the required electrokinetic cell of electric automobile; Also need energy density, therefore researching and developing out high performance anode material of lithium battery has become electrokinetic cell development key place.Wherein, commercial the earliest cobalt acid lithium production technology is the most ripe, and cycle life is good, but there is potential safety hazard in the 4 valency cobalt strong oxidizing properties that its charging back forms, and the actual capacity of cobalt acid lithium has only 148mA/g, and is on the low side with respect to the demand of electrokinetic cell.And cobalt resource is deficient, costs an arm and a leg and has toxicity.The ternary material that is the basis with Ni, Co, Mn in recent years and with LiMn 2O 4For the spinelle shape material of representing has obtained extensive studies, but, restricted their development because there is defective separately in it.Recently, mainly by Li 2MnO 3With stratified material LiMO 2(M=Mn; Ni; Wherein one or more such as Co) solid solution that forms has advantages such as theoretical capacity height, operating voltage is high, cost is low, security performance is good as the rich lithium layered cathode material of lithium battery, is expected to become the anode material of lithium battery of high-energy-density of new generation.But the rich lithium material cycle performance of having reported is poor, and high rate performance is undesirable, has limited its competitive advantage and extensive use.
Summary of the invention
The objective of the invention is to above-mentioned existing problems, provide that a kind of energy density is big, high rate performance is good, cost is low, fail safe is good and the high power capacity of long service life richness lithium layered crystal structure anode material of lithium battery and preparation thereof.
Technical scheme of the present invention:
The rich lithium layered crystal structure of a kind of high power capacity anode material of lithium battery, structure are the particle surface coating one deck LiNbO at Powdered rich lithium layered crystal material 3, the chemical formula of wherein Powdered rich lithium layered crystal material is xLi 2MnO 3(1-x) Li Ni mCo nMn 1-m-nO 2, in the formula: 0.2≤x≤0.9,0.1≤m<1,0≤n≤0.5.
Said LiNbO 3Quality account for the 1-10% of material gross mass.
Said coating layer LiNbO 3Thickness less than 1 μ m.
The preparation method of the rich lithium layered crystal structure of a kind of said high power capacity anode material of lithium battery, step is following:
(1) rich lithium stratiform [xMn (1-x) Ni mCo nMn 1-m-n] [OH] 2The preparation of presoma:
1) with mol ratio Ni:Co:Mn=(1-x) m: (1-x) n: the ratio of [(1-x) (1-m-n)+x] preparation nickel cobalt mn sulphate solution, wherein 0.2≤x≤0.9,0.1≤m 1,0≤n≤0.5; 0 < m+n < 1;
2) speed with 1L/h at the uniform velocity adds the above-mentioned salting liquid for preparing in agitated reactor, is that the sodium hydroxide solution of 2-10M is to carry out coprecipitation reaction under the condition of 10-12 to obtain the presoma solidliquid mixture in the pH value through concentration;
3) after all salting liquids inject agitated reactor fully, stop reaction, solidliquid mixture separates through centrifugal filtration, to neutrality, down dries 4-10h at 80-200 ℃ with deionized water wash, obtains molecular formula and is [xMn (1-x) Ni mCo nMn 1-m-n] [OH] 2, 0.2≤x in the formula≤0.9,0.1≤m<1,0≤n≤0.5,0<m+n<1 presoma;
(2) high temperature solid-state method prepares rich lithium layered crystal structure xLi 2MnO 3(1-x) Li Ni mCo nMn 1-m-nO 2Particle:
1) with above-mentioned presoma and lithium carbonate powder in molar ratio 1:1-2 mix;
2) place Muffle furnace to carry out the multistage roasting said mixture, sintering temperature is 300-1200 ℃, roasting time 8-30h, then through cooling, broken, sieving obtains the powder granule xLi of rich lithium layered crystal structure to be coated 2MnO 3(1-x) Li Ni mCo nMn 1-m-nO 2, 0.2≤x in the formula≤0.9,0.1≤m<1,0≤n≤0.5,0<m+n<1;
(3) use LiNbO 3Coat xLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2Particle:
The powder granule of the rich lithium layered crystal structure that 1) above-mentioned roasting is obtained and ethanol are that the mixing speed that 1:5-20 puts into blender and changes with per minute 50-500 suspends powder granule by mass ratio;
2) take by weighing a certain amount of ethanol niobium and pour in the blender, the consumption of ethanol niobium is with last LiNbO 3The needed ratio of shared product gross mass is calculated definite, and evenly hydrolysis is surperficial in the powder granule of rich lithium layered crystal structure in the ethanol of rotation for the ethanol niobium;
3) take by weighing with the lithium carbonate of the identical stoichiometric proportion of ethanol niobium and add in the blender, it is uniformly dispersed;
4) in the process that stirs, be heated to 80 ℃, be stirred to and be placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block;
5) place Muffle furnace can obtain LiNbO in 10 hours above-mentioned block at 500-800 ℃ of roasting temperature 3The xLi that coats 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The rich lithium layered crystal structure of the high power capacity of particle anode material of lithium battery.
Advantage of the present invention is: this anode material of lithium battery has been compared following advantage with traditional anode material of lithium battery: 1) specific capacity is high, and height ratio capacity can reach 280mAh/g; 2) through LiNbO 3The rich lithium layer structure material that coats with do not coat before compare and show higher charging and discharging capacity and cycle life; 3) under high-voltage large current density, has excellent electrochemical properties more.
Description of drawings
Fig. 1 is the XRD figure before and after embodiment 1 rich lithium layered crystal particle coats.
Fig. 2 is the stereoscan photograph before and after embodiment 1 rich lithium layered crystal particle coats.
Fig. 3 is 300 1C cyclic curve figure before and after embodiment 1 rich lithium layered crystal particle coats.
Fig. 4 is the first charge-discharge curve chart before and after embodiment 1 rich lithium layered crystal particle coats.
Fig. 5 is the first charge-discharge curve chart under the high current charge-discharge condition before and after embodiment 5 rich lithium layered crystal particles coat.
Fig. 6 is 20 0.1C cyclic curve figure before and after embodiment 6 rich lithium layered crystal particles coat.
Embodiment
Embodiment 1:
The preparation method of the rich lithium layered crystal structure of a kind of high power capacity anode material of lithium battery:
1) do not coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Use 2767g nickelous sulfate, 2924g cobaltous sulfate, 7044g manganese sulfate compound concentration salting liquid 25L as 2.5M.It is the agitated reactor of 200rps that the solution for preparing is injected rotating speed with the speed of 1L/h, injects the NaOH solution of 10M simultaneously, notes regulating the aqueous slkali flow velocity, keeps pH value between 10-11, injects agitated reactor fully, the completion of presoma preparation feedback to salting liquid.Solidliquid mixture after the reaction completion through centrifugation, is washed to the neutrality back and dries 6h down at 120 ℃.With presoma and lithium carbonate after the oven dry in molar ratio 1:1.5 mix back 950 ℃ of roasting 16h in Muffle furnace, the material after the roasting is through the sieve powder granule material 0.5Li of the rich lithium layered crystal structure that obtains homogeneous of fragmentation 2MnO 30.5LiNi 1/3Co 1/3Mn 1/3O 2
2) coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Place the quick stirring of blender to make its suspension with an amount of ethanol powder granule material taking-up 9.6 grams of the above-mentioned spherical rich lithium layered crystal structure that makes.Take by weighing 0.8609 gram ethanol niobium and pour in the blender, the ethanol niobium is evenly degraded in the ethanol of high speed rotating in the powder granule surface of the rich lithium layered crystal structure of sphere.Take by weighing 0.1 gram lithium carbonate again and add in the blender, it is uniformly dispersed.In the process that stirs, whole system is heated to 80 ℃, is stirred to and was placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block object.Place 700 ℃ of roastings of Muffle furnace can obtain LiNbO in 10 hours top mixing block 3Coating increases 0.5Li 2MnO 30.5LiNi 1/3Co 1/3Mn 1/3O 2Granular product.Final LiNbO 3Quality account for 4% of gross product, coating layer LiNbO 3Thickness be 20-100nm.
Two kinds of materials are processed 2032 button cells respectively before and after will coating; Be respectively 265mAh/g and 261mAh/g in 2.0-4.8V 0.1C first discharge specific capacity; As shown in Figure 3,300 circulation backs of 2.0-4.8V 1C capability retention is respectively 37.7% and 53.6%, as sees shown in Figure 4; Capability retention is respectively 79% and 88% after 2.0-4.8V 1C circulation under 55 ℃ of high temperature 50 times.
Embodiment 2:
The preparation method of the rich lithium layered crystal structure of a kind of high power capacity anode material of lithium battery:
1) do not coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Use 2767g nickelous sulfate, 2924g cobaltous sulfate, 7044g manganese sulfate compound concentration salting liquid 25L as 2.5M.It is the agitated reactor of 200rps that the solution for preparing is injected rotating speed with the speed of 1L/h, injects the NaOH solution of 10M simultaneously, notes regulating the aqueous slkali flow velocity, keeps pH value between 10-11, injects agitated reactor fully, the completion of presoma preparation feedback to salting liquid.Solidliquid mixture after the reaction completion through centrifugation, is washed to the neutrality back and dries 6h down at 120 ℃.With presoma and lithium carbonate after the oven dry in molar ratio 1:1.5 mix back 950 ℃ of roasting 16h in Muffle furnace, the material after the roasting is through the sieve powder granule material 0.5Li of the rich lithium layered crystal structure that obtains homogeneous of fragmentation 2MnO 30.5LiNi 1/3Co 1/3Mn 1/3O 2
2) coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Place the quick stirring of blender to make its suspension with an amount of ethanol powder granule material taking-up 9.2 grams of the above-mentioned spherical rich lithium layered crystal structure that makes.Take by weighing 1.7219 gram ethanol niobiums and pour in the blender, the ethanol niobium is evenly degraded in the ethanol of high speed rotating in the powder granule surface of the rich lithium layered crystal structure of sphere.Take by weighing 0.2 gram lithium carbonate again and add in the blender, it is uniformly dispersed.In the process that stirs, whole system is heated to 80 ℃, is stirred to and was placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block object.Place 700 ℃ of roastings of Muffle furnace can obtain LiNbO in 10 hours top mixing block 3Coating increases 0.5Li 2MnO 30.5LiNi 1/3Co 1/3Mn 1/3O 2Granular product.Final LiNbO 3Quality account for 8% of gross product, coating layer LiNbO 3Thickness be 30-150nm.
Two kinds of materials are processed 2032 button cells respectively before and after will coating, and are respectively 262.3mAh/g and 243.2mAh/g in 2.0-4.8V 0.1C first discharge specific capacity; 2.0-4.8V 100 circulation backs of 1C capability retention is respectively 77% and 89%; Capability retention is respectively 79% and 90% after 2.0-4.8V 1C circulation under 55 ℃ of high temperature 50 times.
Embodiment 3:
The preparation method of the rich lithium layered crystal structure of a kind of high power capacity anode material of lithium battery:
1) do not coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Use 2767g nickelous sulfate, 2924g cobaltous sulfate, 7044g manganese sulfate compound concentration salting liquid 25L as 2.5M.It is the agitated reactor of 200rps that the solution for preparing is injected rotating speed with the speed of 1L/h, injects the NaOH solution of 10M simultaneously, notes regulating the aqueous slkali flow velocity, keeps pH value between 10-11, injects agitated reactor fully, the completion of presoma preparation feedback to salting liquid.Solidliquid mixture after the reaction completion through centrifugation, is washed to the neutrality back and dries 6h down at 120 ℃.With presoma and lithium carbonate after the oven dry in molar ratio 1:1.5 mix back 950 ℃ of roasting 16h in Muffle furnace, the material after the roasting is through the sieve powder granule material 0.5Li of the rich lithium layered crystal structure that obtains homogeneous of fragmentation 2MnO 30.5LiNi 1/3Co 1/3Mn 1/3O 2
2) coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Place the quick stirring of blender to make its suspension with an amount of ethanol powder granule material taking-up 9.6 grams of the above-mentioned spherical rich lithium layered crystal structure that makes.Take by weighing 0.4305 gram ethanol niobium and pour in the blender, the ethanol niobium is evenly degraded in the ethanol of high speed rotating in the powder granule surface of the rich lithium layered crystal structure of sphere.Take by weighing 0.05 gram lithium carbonate again and add in the blender, it is uniformly dispersed.In the process that stirs, whole system is heated to 80 ℃, is stirred to and was placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block object.Place 700 ℃ of roastings of Muffle furnace can obtain LiNbO in 10 hours top mixing block 3Coating increases 0.5Li 2MnO 30.5LiNi 1/3Co 1/3Mn 1/3O 2Granular product.Final LiNbO 3Quality account for 2% of gross product, coating layer LiNbO 3Thickness be 150-80nm.
Two kinds of materials are processed 2032 button cells respectively before and after will coating, and are respectively 262.3mAh/g and 257.6mAh/g in 2.0-4.8V 0.1C first discharge specific capacity; 2.0-4.8V 100 circulation backs of 1C capability retention is respectively 77% and 83%; Capability retention is respectively 79% and 85% after 2.0-4.8V 1C circulation under 55 ℃ of high temperature 50 times.
Embodiment 4:
The preparation method of the rich lithium layered crystal structure of a kind of high power capacity anode material of lithium battery:
1) do not coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Use 3873g nickelous sulfate, 4192g cobaltous sulfate, 5635g manganese sulfate compound concentration salting liquid 25L as 2.5M.It is the agitated reactor of 200rps that the solution for preparing is injected rotating speed with the speed of 1L/h, injects the NaOH solution of 10M simultaneously, notes regulating the aqueous slkali flow velocity, keeps pH value between 10-11, injects agitated reactor fully, the completion of presoma preparation feedback to salting liquid.Solidliquid mixture after the reaction completion through centrifugation, is washed to the neutrality back and dries 6h down at 120 ℃.With presoma and lithium carbonate after the oven dry in molar ratio 1:1.3 mix back 950 ℃ of roasting 16h in Muffle furnace, the material after the roasting is through the sieve powder granule material 0.3Li of the rich lithium layered crystal structure that obtains homogeneous of fragmentation 2MnO 30.7LiNi 1/3Co 1/3Mn 1/3O 2
2) coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Place the quick stirring of blender to make its suspension with an amount of ethanol powder granule material taking-up 9.6 grams of the above-mentioned spherical rich lithium layered crystal structure that makes.Take by weighing 0.8609 gram ethanol niobium and pour in the blender, the ethanol niobium is evenly degraded in the ethanol of high speed rotating in the powder granule surface of the rich lithium layered crystal structure of sphere.Take by weighing 0.1 gram lithium carbonate again and add in the blender, it is uniformly dispersed.In the process that stirs, whole system is heated to 80 ℃, is stirred to and was placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block object.Place 700 ℃ of roastings of Muffle furnace can obtain LiNbO in 10 hours top mixing block 3Coating increases 0.3Li 2MnO 30.7LiNi 1/3Co 1/3Mn 1/3O 2Granular product.Final LiNbO 3Quality account for 4% of gross product, coating layer LiNbO 3Thickness be 20-100nm.
Two kinds of materials are processed 2032 button cells respectively before and after will coating, and are respectively 285.7mAh/g and 271.9mAh/g in 2.0-4.8V 0.1C first discharge specific capacity; 2.0-4.8V 100 circulation backs of 1C capability retention is respectively 73% and 86%; Capability retention is respectively 75% and 84% after 2.0-4.8V 1C circulation under 55 ℃ of high temperature 50 times.
Embodiment 5:
The preparation method of the rich lithium layered crystal structure of a kind of high power capacity anode material of lithium battery:
1) do not coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Use 1660g nickelous sulfate, 1797g cobaltous sulfate, 8452g manganese sulfate compound concentration salting liquid 25L as 2.5M.It is the agitated reactor of 200rps that the solution for preparing is injected rotating speed with the speed of 1L/h, injects the NaOH solution of 10M simultaneously, notes regulating the aqueous slkali flow velocity, keeps pH value between 10-11, injects agitated reactor fully, the completion of presoma preparation feedback to salting liquid.Solidliquid mixture after the reaction completion through centrifugation, is washed to the neutrality back and dries 6h down at 120 ℃.With presoma and lithium carbonate after the oven dry in molar ratio 1:1.7 mix back 950 ℃ of roasting 16h in Muffle furnace, the material after the roasting is through the sieve powder granule material 0.7Li of the rich lithium layered crystal structure that obtains homogeneous of fragmentation 2MnO 30.3LiNi 1/3Co 1/3Mn 1/3O 2
2) coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Place the quick stirring of blender to make its suspension with an amount of ethanol powder granule material taking-up 9.6 grams of the above-mentioned spherical rich lithium layered crystal structure that makes.Take by weighing 0.8609 gram ethanol niobium and pour in the blender, the ethanol niobium is evenly degraded in the ethanol of high speed rotating in the powder granule surface of the rich lithium layered crystal structure of sphere.Take by weighing 0.1 gram lithium carbonate again and add in the blender, it is uniformly dispersed.In the process that stirs, whole system is heated to 80 ℃, is stirred to and was placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block object.Place 700 ℃ of roastings of Muffle furnace can obtain LiNbO in 10 hours top mixing block 3Coating increases 0.7Li 2MnO 30.3LiNi 1/3Co 1/3Mn 1/3O 2Granular product.Final LiNbO 3Quality account for 4% of gross product, coating layer LiNbO 3Thickness be 20-100nm.
2.0-4.8V 0.1C first discharge specific capacity was respectively 252.3mAh/g and 247.6mAh/g after two kinds of materials were processed 2032 button cells respectively before and after will coating; 2.0-4.8V 100 circulation backs of 1C capability retention is respectively 81% and 87%; 2.0-4.8V the 3C first discharge specific capacity is respectively 159.3mAh/g and 178.6mAh/g, as sees shown in Figure 5ly, high rate performance obviously improves; Capability retention is respectively 83% and 90% after 3.0-4.3V 1C circulation under 55 ℃ of high temperature 50 times.
Embodiment 6:
The preparation method of the rich lithium layered crystal structure of a kind of high power capacity anode material of lithium battery:
1) do not coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Use 5809g nickelous sulfate, 6868g manganese sulfate compound concentration salting liquid 25L as 2.5M.It is the agitated reactor of 200rps that the solution for preparing is injected rotating speed with the speed of 1L/h, injects the NaOH solution of 10M simultaneously, notes regulating the aqueous slkali flow velocity, keeps pH value between 10-11, injects agitated reactor fully, the completion of presoma preparation feedback to salting liquid.Solidliquid mixture after the reaction completion through centrifugation, is washed to the neutrality back and dries 6h down at 120 ℃.With presoma and lithium carbonate after the oven dry in molar ratio 1:1.3 mix back 950 ℃ of roasting 16h in Muffle furnace, the material after the roasting is through the sieve powder granule material 0.3Li of the rich lithium layered crystal structure that obtains homogeneous of fragmentation 2MnO 30.7LiNi 0.5Mn 0.5O 2
2) coat LiNbO 3XLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The preparation of particle:
Place the quick stirring of blender to make its suspension with an amount of ethanol powder granule material taking-up 9.6 grams of the above-mentioned spherical rich lithium layered crystal structure that makes.Take by weighing 0.8609 gram ethanol niobium and pour in the blender, the ethanol niobium is evenly degraded in the ethanol of high speed rotating in the powder granule surface of the rich lithium layered crystal structure of sphere.Take by weighing 0.1 gram lithium carbonate again and add in the blender, it is uniformly dispersed.In the process that stirs, whole system is heated to 80 ℃, is stirred to and was placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block object.Place 700 ℃ of roastings of Muffle furnace can obtain LiNbO in 10 hours top mixing block 3Coating increases 0.3Li 2MnO 30.7LiNi 0.5Mn 0.5O 2Granular product.Final LiNbO 3Quality account for 4% of gross product, coating layer LiNbO 3Thickness be 20-100nm.
Two kinds of materials are processed 2032 button cells respectively before and after will coating, and are respectively 244.5mAh/g and 239.6mAh/g in 2.0-4.8V 0.1C first discharge specific capacity; 2.0-4.8V 20 circulation backs of 0.1C capability retention is respectively 88.1% and 94.5%, as shown in Figure 6, cycle performance obviously improves; Capability retention is respectively 83% and 90% after 3.0-4.3V 1C circulation under 55 ℃ of high temperature 20 times.
In sum, LiNbO 3Clad material with compare, the many aspects in cyclical stability, high temperature cyclic performance and the thermal stability aspect have comparatively significantly performance improvement.
Although invention has been described for top combination figure; But the present invention is not limited to above-mentioned embodiment, and above-mentioned embodiment only is schematically, rather than restrictive; Those of ordinary skill in the art is under enlightenment of the present invention; Under the situation that does not break away from aim of the present invention, can also make a lot of distortion, these all belong within the protection of the present invention.

Claims (4)

1. the rich lithium layered crystal structure of high power capacity anode material of lithium battery, it is characterized in that: structure coats one deck LiNbO for the particle surface at Powdered rich lithium layered crystal material 3, the chemical formula of wherein Powdered rich lithium layered crystal material is xLi 2MnO 3(1-x) Li Ni mCo nMn 1-m-nO 2, in the formula: 0.2≤x≤0.9,0.1≤m<1,0≤n≤0.5.
2. according to the rich lithium layered crystal structure of the said high power capacity of claim 1 anode material of lithium battery, it is characterized in that: said LiNbO 3Quality account for the 1-10% of material gross mass.
3. according to the rich lithium layered crystal structure of the said high power capacity of claim 1 anode material of lithium battery, it is characterized in that: said coating layer LiNbO 3Thickness less than 1 μ m.
4. preparation method of the rich lithium layered crystal structure of high power capacity anode material of lithium battery according to claim 1 is characterized in that step is following:
(1) rich lithium stratiform [xMn (1-x) Ni mCo nMn 1-m-n] [OH] 2The preparation of presoma:
1) with mol ratio Ni:Co:Mn=(1-x) m: (1-x) n: the ratio of [(1-x) (1-m-n)+x] preparation nickel cobalt mn sulphate solution, wherein 0.2≤x≤0.9,0.1≤m 1,0≤n≤0.5; 0 < m+n < 1;
2) speed with 1L/h at the uniform velocity adds the above-mentioned salting liquid for preparing in agitated reactor, is that the sodium hydroxide solution of 2-10M is to carry out coprecipitation reaction under the condition of 10-12 to obtain the presoma solidliquid mixture in the pH value through concentration;
3) after all salting liquids inject agitated reactor fully, stop reaction, solidliquid mixture separates through centrifugal filtration, to neutrality, down dries 4-10h at 80-200 ℃ with deionized water wash, obtains molecular formula and is [xMn (1-x) Ni mCo nMn 1-m-n] [OH] 2, 0.2≤x in the formula≤0.9,0.1≤m<1,0≤n≤0.5,0<m+n<1 presoma;
(2) high temperature solid-state method prepares rich lithium layered crystal structure xLi 2MnO 3(1-x) Li Ni mCo nMn 1-m-nO 2Particle:
1) with above-mentioned presoma and lithium carbonate powder in molar ratio 1:1-2 mix;
2) place Muffle furnace to carry out the multistage roasting said mixture, sintering temperature is 300-1200 ℃, roasting time 8-30h, then through cooling, broken, sieving obtains the powder granule xLi of rich lithium layered crystal structure to be coated 2MnO 3(1-x) Li Ni mCo nMn 1-m-nO 2, 0.2≤x in the formula≤0.9,0.1≤m<1,0≤n≤0.5,0<m+n<1;
(3) use LiNbO 3Coat xLi 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2Particle:
The powder granule of the rich lithium layered crystal structure that 1) above-mentioned roasting is obtained and ethanol are that the mixing speed that 1:5-20 puts into blender and changes with per minute 50-500 suspends powder granule by mass ratio;
2) take by weighing a certain amount of ethanol niobium and pour in the blender, the consumption of ethanol niobium is with last LiNbO 3The needed ratio of shared product gross mass is calculated definite, and evenly hydrolysis is surperficial in the powder granule of rich lithium layered crystal structure in the ethanol of rotation for the ethanol niobium;
3) take by weighing with the lithium carbonate of the identical stoichiometric proportion of ethanol niobium and add in the blender, it is uniformly dispersed;
4) in the process that stirs, be heated to 80 ℃, be stirred to and be placed in the baking oven 100 ℃ of dryings after ethanol volatilizees fully 5 hours, obtain block;
5) place Muffle furnace can obtain LiNbO in 10 hours above-mentioned block at 500-800 ℃ of roasting temperature 3The xLi that coats 2MnO 3(1-x) LiNi mCo nMn 1-m-nO 2The rich lithium layered crystal structure of the high power capacity of particle anode material of lithium battery.
CN2012101890016A 2012-06-08 2012-06-08 High-capacity lithium-rich layered crystalline structured lithium battery cathode material and preparation thereof Pending CN102694165A (en)

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