CN103187596A - Stabilization method for lithium-enriched composite anode material with high specific capacity - Google Patents

Stabilization method for lithium-enriched composite anode material with high specific capacity Download PDF

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CN103187596A
CN103187596A CN2011104445513A CN201110444551A CN103187596A CN 103187596 A CN103187596 A CN 103187596A CN 2011104445513 A CN2011104445513 A CN 2011104445513A CN 201110444551 A CN201110444551 A CN 201110444551A CN 103187596 A CN103187596 A CN 103187596A
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positive pole
stabilization method
lithium composite
composite positive
rich lithium
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顾海涛
黄莉
罗英
谢朝香
王可
汤卫平
解晶莹
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Shanghai Institute of Space Power Sources
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Shanghai Institute of Space Power Sources
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a stabilization method for a lithium-enriched composite anode material with a high specific capacity. The stabilization method comprises the following steps of: step 1, setting a charge cut-off voltage to be in a low-voltage range, and performing charge-discharge cycles; and step 2, setting a charge cut-off voltage to be in a high-voltage range, and performing charge-discharge cycles. The stabilization method for a lithium-enriched composite anode material with a high specific capacity disclosed by the invention adopts a step-type charge-discharge method, so that the non-reversible capacity loss of the lithium-enriched composite anode material is reduced, and the cycle stability is remarkably improved, thus achieving the purpose of stabilizing the lithium-enriched composite anode material.

Description

The stabilization method of the rich lithium composite positive pole of height ratio capacity
 
Technical field
The present invention relates to the anode material for lithium-ion batteries field, relate in particular to the stabilization method of the rich lithium composite positive pole of a kind of height ratio capacity.
 
Background technology
Lithium ion battery is since last century, the nineties was come out, and through the develop rapidly of more than ten years, present technology is comparative maturity, and battery preparation technique is day by day accurately with perfect, by optimizing the energy density that preparation technology has been difficult to increase substantially battery again.People mainly reach this purpose by following several measures at present: adopt the height ratio capacity electrode material; Adopt the high working voltage electrode material; Improve the battery charge cut-ff voltage; Design novel battery structure.Wherein, adopting the height ratio capacity electrode material is the emphasis that people pay close attention to.
LiCoO 2Capacity only be its theoretical capacity 50% (~ 140mAh/g), and exist problems such as resource and fail safe; The LiMn of spinel-type 2O 4LiFePO with olivine-type 4Also obtain business-like application, but with respect to LiCoO 2, both energy densities of back obviously do not improve yet.A kind of by Li[Li 1/3Mn 2/3] O 2With stratiform LiMO 2The rich lithium composite positive pole that (M=Mn, Ni, Co etc.) form is owing to having higher specific capacity (〉 250mAh/g) cause widely and pay close attention to.
Rich lithium composite positive pole xLi 2MnO 3-(1-x) LiMO 2The charge-discharge mechanism of (0＜x≤0.7, M=Mn, Ni, Co etc.) is shown in following equation:
Charging:
<4.5?V?xLi 2MnO 3-(1-x)LiMO 2→xLi 2MnO 3-(1-x)MO 2+(1-x)Li
>4.5?V?xLi 2MnO 3-(1-x)MO 2→xMnO 2-(1-x)MO 2+xLi 2O
Discharge:
xMnO 2-(1-x)MO 2+Li→xLiMnO 2-(1-x)LiMO 2
The main cause that studies show that rich lithium composite positive pole generation irreversible capacity loss and cyclical stability difference is the side reaction that positive electrode and electrolyte take place in the generation in charging oxygen room, back and lithium ion room and the charging process.At present, the main purpose that adopts surface coated method to reach rich lithium composite positive pole stabilisation, but its complex procedures have limited the industrialization process of this material to a certain extent, therefore, demand developing a kind of simple rich lithium composite positive pole stabilization method urgently.
                                                                                              
Summary of the invention
The objective of the invention is at existing rich lithium composite positive pole shortcoming such as big, the cyclical stability difference of irreversible capacity loss first, the stabilization method of the rich lithium composite positive pole of a kind of height ratio capacity is provided, this stabilization method is based on the characteristics of rich lithium composite positive pole component, the method that adopts phase step type to discharge and recharge, rich lithium composite positive pole irreversible capacity loss is reduced, cyclical stability significantly improves, thereby reaches the purpose of stablizing rich lithium composite positive pole.
In order to reach the foregoing invention purpose, the invention provides the stabilization method of the rich lithium composite positive pole of a kind of height ratio capacity, may further comprise the steps: step 1, the cut-ff voltage that will charge is set in the low voltage range, carries out charge and discharge cycles; Step 2, the cut-ff voltage that will charge is set in the high voltage range, carries out charge and discharge cycles.
The stabilization method of above-mentioned rich lithium composite positive pole, wherein, described low voltage range is 4-4.5V, described high voltage range is 4.6-5V.
The stabilization method of above-mentioned rich lithium composite positive pole wherein, in the described step 1, is 0.05C-0.3C with the multiplying power, carries out charge and discharge cycles, and discharge cut-off voltage is 1-3V, and cycle-index is 1-10 time.
The stabilization method of above-mentioned rich lithium composite positive pole wherein, in the described step 2, is 0.05C-0.3C with the multiplying power, carries out charge and discharge cycles, and discharge cut-off voltage is 1-3V, and cycle-index is 1-10 time.
The stabilization method of above-mentioned rich lithium composite positive pole, wherein, the chemical formula of described rich lithium composite positive pole is xLi 2MnO 3-(1-x) LiMO 2, wherein, 0＜x≤0.7, M is Mn, Ni or Co.
The stabilization method of the rich lithium composite positive pole of the height ratio capacity of the present invention cut-ff voltage that will charge earlier is set in the low voltage range, battery is carried out charge and discharge cycles, the cut-ff voltage that will charge again is set in the high voltage range, battery is carried out charge and discharge cycles, the activation method that namely adopts phase step type to discharge and recharge makes rich lithium composite positive pole have advantages such as excellent chemical property and cyclical stability; Simple, the good reproducibility, with low cost of the stabilization method technology of the rich lithium composite positive pole of height ratio capacity of the present invention.
 
Description of drawings
The stabilization method of the rich lithium composite positive pole of height ratio capacity of the present invention is provided by following embodiment and accompanying drawing.
Fig. 1 is the cycle performance of stabilisation sample and stabilisation sample not schematic diagram relatively in the button cell sample in the embodiment of the invention one;
Fig. 2 is the cycle performance schematic diagram of stabilisation sample in the soft-package battery sample in the embodiment of the invention two.
 
Embodiment
Below with reference to Fig. 1～Fig. 2 the stabilization method of the rich lithium composite positive pole of height ratio capacity of the present invention is described in further detail.
Embodiment one
Present embodiment is example with the button cell, and this button cell utilizes rich lithium composite positive pole to make positive electrode, before the stabilization method that describes the use present embodiment in detail is handled this button cell, introduces the preparation method of this button cell earlier:
The preparation of rich lithium composite positive pole: be 0.467:0.2:0.2 by Mn, Ni, Co metal ion mole ratio, manganese sulfate, nickelous sulfate, cobaltous sulfate are dissolved in the deionized water, are made into Mn, Ni, Co metal ion total concentration is the homogeneous transparent metal ion solution of 2mol/L; Prepare the polyacrylamide solution of 0.2 mol/L, 1.2 times sodium carbonate of stoichiometric proportion consumption is joined in the polyacrylamide solution, obtain the mixed precipitation agent solution of polyacrylamide and sodium carbonate; Precipitant solution slowly is added drop-wise in the metal ion solution, carries out coprecipitation reaction; Precipitated product obtains the carbonate precursor through filtration, cleaning, drying; The carbonate precursor is mixed with 1.02 times lithium carbonate ball milling of stoichiometric proportion consumption, through 900 ℃, be incubated 10 h, obtain Li 1.133Mn 0.467Ni 0.2Co 0.2O 2Rich lithium composite positive pole.
The preparation of button cell: 90 gram N-methyl pyrrolidones and 4.75 gram polyvinylidene fluoride are mixed the viscosity variation of stirring mixed liquor within 10 minutes less than 3%, add 3.5 gram particles footpaths again and be stirred to less than 2 microns microspheroidal superconduction carbon black and 1.75 gram flakey electrically conductive graphites that mixture viscosity changes less than 3% within 10 minutes, add the rich lithium composite positive pole Li of 90 grams at last 1.133Mn 0.467Ni 0.2Co 0.2O 2Stirring mixture viscosity within 10 minutes changes less than 5%, then above-mentioned solidliquid mixture is coated on the aluminium foil, and 110 ℃ of vacuumizes obtained positive electrode after 24 hours;
Adopt the CR2016 battery case, with Li 1.133Mn 0.467Ni 0.2Co 0.2O 2Be positive pole, the lithium sheet is negative pole, 1 M LiPF 6(EC:EMC=3:7) be electrolyte, make button cell.
After preparing button cell, use the stabilization method of the rich lithium composite positive pole of height ratio capacity of present embodiment that this button cell is handled, concrete steps are as follows:
With 0.1C(25 mA/g) be the density of charging current, the charging cut-ff voltage is 4.5V, is discharge current density with 0.1C (25 mA/g), and discharge cut-off voltage is 2V, carries out charge and discharge cycles, and cycle-index is 5 times; After treating that above-mentioned circulation is finished, with 0.1C(25 mA/g) be the density of charging current, the charging cut-ff voltage is 4.8V, with 0.1C(25 mA/g) be discharge current density, discharge cut-off voltage is 2V, carries out charge and discharge cycles, cycle-index is 2 times, and rich lithium composite positive pole is carried out stabilization processes.
The stabilization method of the rich lithium composite positive pole of the present embodiment height ratio capacity cut-ff voltage that will charge earlier is set in the low voltage range (4-4.5V), battery is carried out charge and discharge cycles, the cut-ff voltage that will charge again is set in the high voltage range (4.6-5V), battery is carried out charge and discharge cycles, the activation method that namely adopts phase step type to discharge and recharge.
Carry out the charge-discharge performance test to the button cell sample a after handling through the present embodiment stabilization method and without the button cell sample b that stabilization method is handled, test parameter is as follows: with 0.1C(25 mA/g) be the density of charging current, the charging cut-ff voltage is 4.8V, be discharge current density with 0.1C (25 mA/g), discharge cut-off voltage is 2V, carry out charge and discharge cycles, the charge-discharge performance of two samples as shown in Figure 1, circulate after 50 times, the capability retention of sample a is 95%, and the capability retention of sample b is 82%; Circulate after 100 times, the capability retention of sample a is 90%, and through more as can be known, after the stabilized processing, the cyclical stability of rich lithium composite positive pole significantly improves.
 
Embodiment two
Present embodiment is example with the soft-package battery, and this soft-package battery utilizes rich lithium composite positive pole to make positive electrode, and in the process of preparation soft-package battery, the preparation of rich lithium composite positive pole and positive plate does not repeat them here with embodiment one.
Being prepared as of soft-package battery: 100 gram distilled water and 1.5 gram sodium carboxymethylcelluloses are mixed the viscosity variation of stirring mixed liquor within 10 minutes less than 3%, add 2.0 gram particles footpaths then and be stirred to less than 3 microns microspheroidal superconduction carbon black that mixture viscosity changes less than 3% within 10 minutes, adding 95 gram graphite cathodes stirrings mixture viscosity within 10 minutes again changes less than 3%, adding 1.5g butadiene-styrene rubber (SBR) stirring mixture viscosity in 10 minutes then changes less than 3%, at last above-mentioned solidliquid mixture is coated on the Copper Foil, the preparation negative electrode is dried in 100 ℃ of vacuumizes after 8 hours;
The positive and negative electrode of above-mentioned making is cut into the small pieces of definite shape, some positive and negative electrode small pieces are piled up successively with the both positive and negative polarity over-over mode, insulate with barrier film between the positive and negative electrode, and weld aluminium strip at aluminium foil respectively, weld nickel strap on the Copper Foil, and finally use adhesive tape fixedly positive and negative electrode make positive and negative electrode avoid electron conduction, make electric core, then, electric core is put into external packing, remove moisture in a vacuum;
In the dewatered external packing that electric core is housed, add 4g electrolyte (1 M LiPF 6, EC:EMC=3:7), seal and leave standstill, make electrolyte fully soak into solid particle on aluminium foil and the Copper Foil, change into, and sealing exhaust body passage, obtain the Soft Roll lithium-ions battery.
After preparing soft-package battery, use the stabilization method of the rich lithium composite positive pole of height ratio capacity of present embodiment that this soft-package battery is handled, concrete steps are as follows:
With 0.1C(25 mA/g) be the density of charging current, the charging cut-ff voltage is 4.4V, with 0.1C(25 mA/g) and be discharge current density, discharge cut-off voltage is 2V, carries out charge and discharge cycles, cycle-index is 2 times; After treating that above-mentioned circulation is finished, with 0.1C(25 mA/g) be the density of charging current, the charging cut-ff voltage is 4.6V, with 0.1C(25 mA/g) be discharge current density, discharge cut-off voltage is 2V, carries out charge and discharge cycles, cycle-index is 2 times, and rich lithium composite positive pole is carried out stabilization processes.
The stabilization method of the rich lithium composite positive pole of the present embodiment height ratio capacity cut-ff voltage that will charge earlier is set in the low voltage range (4-4.5V), battery is carried out charge and discharge cycles, the cut-ff voltage that will charge again is set in the high voltage range (4.6-5V), battery is carried out charge and discharge cycles, the activation method that namely adopts phase step type to discharge and recharge.
Soft-package battery after handling through the present embodiment stabilization method is carried out the charge-discharge performance test, test parameter is as follows: with 0.1C(25 mA/g) be the density of charging current, the charging cut-ff voltage is 4.6V, with 0.1C(25 mA/g) be discharge current density, discharge cut-off voltage is 2V, and experiment shows, after the cycle performance circulation 50 times, capability retention is 94%, as shown in Figure 2.

Claims (5)

1. the stabilization method of the rich lithium composite positive pole of height ratio capacity is characterized in that, may further comprise the steps:
Step 1, the cut-ff voltage that will charge is set in the low voltage range, carries out charge and discharge cycles;
Step 2, the cut-ff voltage that will charge is set in the high voltage range, carries out charge and discharge cycles.
2. the stabilization method of rich lithium composite positive pole as claimed in claim 1 is characterized in that, described low voltage range is 4-4.5V, and described high voltage range is 4.6-5V.
3. the stabilization method of rich lithium composite positive pole as claimed in claim 1 is characterized in that, in the described step 1, is 0.05C-0.3C with the multiplying power, carries out charge and discharge cycles, and discharge cut-off voltage is 1-3V, and cycle-index is 1-10 time.
4. the stabilization method of rich lithium composite positive pole as claimed in claim 1 is characterized in that, in the described step 2, is 0.05C-0.3C with the multiplying power, carries out charge and discharge cycles, and discharge cut-off voltage is 1-3V, and cycle-index is 1-10 time.
5. the stabilization method of rich lithium composite positive pole as claimed in claim 1 is characterized in that, the chemical formula of described rich lithium composite positive pole is xLi 2MnO 3-(1-x) LiMO 2, wherein, 0＜x≤0.7, M is Mn, Ni or Co.
CN2011104445513A 2011-12-28 2011-12-28 Stabilization method for lithium-enriched composite anode material with high specific capacity Pending CN103187596A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019095530A1 (en) * 2017-11-20 2019-05-23 中国科学院宁波材料技术与工程研究所 Lithium-rich oxide positive electrode material, preparation method therefor, and lithium ion battery
CN113497288A (en) * 2020-03-19 2021-10-12 宁德新能源科技有限公司 Charging method, electronic device, and storage medium

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Publication number Priority date Publication date Assignee Title
CN101501920A (en) * 2006-09-29 2009-08-05 三井金属矿业株式会社 Non-aqueous electrolyte secondary battery
CN101783424A (en) * 2009-01-15 2010-07-21 深圳市比克电池有限公司 Method for pre-charging lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101501920A (en) * 2006-09-29 2009-08-05 三井金属矿业株式会社 Non-aqueous electrolyte secondary battery
CN101783424A (en) * 2009-01-15 2010-07-21 深圳市比克电池有限公司 Method for pre-charging lithium ion battery

Non-Patent Citations (1)

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Title
ATSUSHI ITO ET AL: "A new approach to improve the high-voltage cyclic performance of Li-rich layered cathode material by electrochemical pre-treatment", 《JOURNAL OF POWER SOURCES》, vol. 183, no. 1, 15 August 2008 (2008-08-15), pages 344 - 346 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019095530A1 (en) * 2017-11-20 2019-05-23 中国科学院宁波材料技术与工程研究所 Lithium-rich oxide positive electrode material, preparation method therefor, and lithium ion battery
CN113497288A (en) * 2020-03-19 2021-10-12 宁德新能源科技有限公司 Charging method, electronic device, and storage medium
CN113497288B (en) * 2020-03-19 2022-12-13 宁德新能源科技有限公司 Charging method, electronic device, and storage medium

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Application publication date: 20130703