CN102354740B - Preparation method and application of negative pole material of lithium battery - Google Patents
Preparation method and application of negative pole material of lithium battery Download PDFInfo
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- CN102354740B CN102354740B CN2011102898307A CN201110289830A CN102354740B CN 102354740 B CN102354740 B CN 102354740B CN 2011102898307 A CN2011102898307 A CN 2011102898307A CN 201110289830 A CN201110289830 A CN 201110289830A CN 102354740 B CN102354740 B CN 102354740B
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Abstract
The invention relates to a negative pole composite material of a lithium battery, and the negative pole composite material is prepared from silicon carbide micro-powder, copper powder, aluminum powder, graphite powder and the like in a certain proportion. The invention further relates to a preparation method of the negative pole composite material of the lithium battery, the method is simple and effective in process, the intermediate trivial flow process steps are omitted, and the preparation method is more environmentally-friendly and simpler. The negative pole material prepared by the preparation method has the advantages of high charge-discharge efficiency, good cycle performance and the like, and further has extensive application value.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of cathode of lithium battery composite material, belong to electrochemical field.
Background technology
Lithium battery is that a class is negative material, the battery that uses non-aqueous electrolytic solution by lithium metal or lithium alloy.The lithium battery occurred the earliest comes from great inventor Edison, uses following reaction: Li+MnO2=LiMnO2 should react for redox reaction, electric discharge.Because the chemical characteristic of lithium metal is very active, make processing, preservation, the use of lithium metal, very high to environmental requirement.At present, growing along with mobile electronic equipment to high power capacity, long-life batteries demand, people have higher requirement to the performance of lithium ion battery.Because the chemical characteristic of lithium metal is very active, make processing, preservation, the use of lithium metal, very high to environmental requirement, so lithium battery production will be carried out under special environmental condition.The lithium battery major advantage: energy Ratios is higher, has reached at present 460-600Wh/kg, is approximately 6-7 times of lead-acid battery; Long service life, can reach more than 6 years useful life; Rated voltage high (the monomer operating voltage is 3.7V or 3.2V), approximate the series voltage of 3 NI-Gs or nickel-hydrogen chargeable cell, is convenient to form the battery supply group; Possess high power and bear pressure, wherein the ferrous phosphate lithium ion battery of used for electric vehicle can reach the ability that 15-30C discharges and recharges, and is convenient to high-intensity Acceleration of starting; Self-discharge rate is very low, and this is one of the most outstanding superiority of this battery, generally can accomplish at present below 1%/moon, less than 1/20 of Ni-MH battery; Environmental protection, no matter produce, use and scrap, do not contain, do not produce yet poisonous and harmful heavy metallic element and the materials such as any lead, mercury, cadmium.Due to the lot of advantages of lithium battery, lithium battery is widely used on electronic instrument, number and household appliances.
But capacity of lithium ion battery is on the low side has become a bottleneck of restriction battery industry development, find the more positive electrode of height ratio capacity and the developing direction that negative material has become the battery material field.Since early 1990s, Sony Corporation released business-like lithium ion battery, the specific capacity of positive electrode is always relatively on the low side, and this problem does not have large breakthrough all the time, and its research focus is to find new positive electrode system, reduce the cost of positive electrode, improve the security performance of positive electrode.Current business-like negative material is carbon, and since the lithium ion battery commercialization, the research of material with carbon element has obtained significant progress, and actual specific capacity improves very fast, has approached the theoretical value of 372mAhPg, is difficult to have the space of lifting again.Finding the negative material that substitutes carbon becomes an important developing direction, and the material theoretical specific capacity higher with it such as Si, Sn, Al, Sb are subject to attracting attention of lithium ion battery material circle.
Silicon has lot of advantages, and on the earth, reserves are abundant, cost is lower, environmental sound.Silicon and lithium can form alloy, have 4 kinds of phase: Li12Si7, Li13 Si4, Li7 Si3 and Li22 Si5.Silicon has higher theoretical specific capacity (Li22 Si5:4200mAhPg) and lower embedding lithium current potential (vsLi+PLi), thereby is a kind of very rising lithium ion battery negative material.Yet, in charge and discharge process, the reaction of the removal lithium embedded of silicon will be followed 310% change in volume, easily cause that electrode cracking and active material come off, thereby cause the electrode cycle performance to worsen.One of thinking addressed this problem is the synthesis of silica-base compound, the volumetric expansion of buffer electrode, the cyclical stability of raising electrode.
Summary of the invention
The technical issues that need to address of the present invention are, overcome the deficiencies in the prior art part, and a kind of preparation method of cathode of lithium battery composite material is provided, and the negative material prepared by the method possesses the advantages such as efficiency for charge-discharge is high, good cycle.
The objective of the invention is to be achieved through the following technical solutions: a kind of preparation method of cathode of lithium battery composite material comprises the steps:
1) silicon carbide micro-powder, copper powder, aluminium powder, graphite powder were according to weight ratio 10: 2: 1: 1 ratio mix and blend 30 minutes.
2) ball grinder carries out vent gas, and be filled with argon gas, by step 1) mixed material that the obtains ball-milling treatment of carrying out 60 hours of packing in ball grinder makes composite material, wherein ball grinder adopts the polyurethane grinding jar, abrading-ball is natural agate, take absolute ethyl alcohol as ball-milling medium, and ball material weight ratio is 8: 1.
3) in step 2) obtain in composite material and add 75% ethanol; wherein the ratio of composite material and 75% ethanol is 1 gram: 1.5 milliliters; stir and make mixture; then the ratio that is 10: 1 according to mixture and PVP K-30 weight ratio adds PVP K-30 as coalescents; stirring makes slurry; coat on round copper sheet; then under 60 ℃, place 15 hours; carry out annealing in process; after water cooling, dry cutting under 100 ℃; finally 600 ℃ of sintering 4 hours under argon shield atmosphere, obtain negative electrode material of the present invention.
Described silicon carbide powder preferably is prepared from accordance with the following steps: the carborundum section sand that to choose particle diameter be 3mm, then deironing, de-carbon, carry out alkali cleaning, airing is also dried, and then carries out the airflow milling pulverizing, then with the dressing sieve net in different orders footpath, is sieved, particle diameter is at 15-16um and two kinds of silicon carbide micro-powders of 29-30um, finally two kinds of silicon carbide micro-powders are mixed and get final product according to the ratio of 1: 1, wherein the content of di-iron trioxide is controlled in 0.05%, and the content of carbon is controlled in 0.05%.
Described copper powder, preferably by copper sheet ball milling 30 hours, is then crossed 200 mesh sieves and is obtained.
Described aluminium powder, preferably by aluminium flake ball milling 12 hours, is then crossed 200 mesh sieves and is obtained.
Described graphite powder, preferably its particle diameter is 300 orders.
The condition of described annealing in process is preferably: temperature is 420 ℃, and temperature retention time is 120 seconds, and annealing atmosphere is selected the mixed atmosphere of nitrogen and krypton, and the two volume ratio is 4: 1.
Preparation technology of the present invention is simply effective, by the shirtsleeve operation step, can obtain desirable negative material, loaded down with trivial details process step in the middle of having saved, and more environmental protection is simple and easy.
The negative material that the present invention prepares possesses the advantages such as efficiency for charge-discharge is high, good cycle, is with a wide range of applications.
Embodiment
Embodiment 1
The preparation method of cathode of lithium battery composite material, comprise the steps:
1) silicon carbide micro-powder, copper powder, aluminium powder, graphite powder were according to weight ratio 10: 2: 1: 1 ratio mix and blend 30 minutes.
2) ball grinder carries out vent gas, and be filled with argon gas, by step 1) mixed material that the obtains ball-milling treatment of carrying out 60 hours of packing in ball grinder makes composite material, wherein ball grinder adopts the polyurethane ball grinder, abrading-ball is natural agate, take absolute ethyl alcohol as ball-milling medium, and abrading-ball and composite material weight ratio are 8: 1.
3) in step 2) obtain in composite material and add 75% ethanol (V/V); wherein the ratio of composite material and 75% ethanol is 1 gram: 1.5 milliliters; stir and make mixture; then the ratio that is 10: 1 according to mixture and PVP K-30 weight ratio adds PVP K-30 as coalescents; stirring makes slurry; coat on round copper sheet; then under 60 ℃, place 15 hours; carry out annealing in process; after water cooling, dry cutting under 100 ℃; finally 600 ℃ of sintering 4 hours under argon shield atmosphere, obtain negative electrode material.
Embodiment 2
1) raw-material preparation: be prepared from accordance with the following steps: the carborundum section sand that to choose particle diameter be 3mm, then deironing, de-carbon, carry out alkali cleaning, airing is also dried, then carry out the airflow milling pulverizing, then with the dressing sieve net in different orders footpath, sieved, particle diameter is at 15-16um and two kinds of silicon carbide micro-powders of 29-30um, finally two kinds of silicon carbide micro-powders are mixed according to the ratio of 1: 1 and obtain silicon carbide micro-powder required for the present invention, wherein the content of di-iron trioxide is controlled in 0.05%, and the content of carbon is controlled in 0.05%.Copper powder, by copper sheet ball milling 30 hours, is then crossed 200 mesh sieves and is obtained.Aluminium powder, by aluminium flake ball milling 12 hours, is then crossed 200 mesh sieves and is obtained.The graphite powder particle diameter is 300 orders.By the above-mentioned silicon carbide micro-powder prepared, copper powder, aluminium powder, graphite powder according to weight ratio 10: 2: 1: 1 ratio mix and blend 30 minutes.
2) ball grinder carries out vent gas, and be filled with argon gas, by step 1) mixed material that the obtains ball-milling treatment of carrying out 60 hours of packing in ball grinder makes composite material, wherein ball grinder adopts the polyurethane ball grinder, abrading-ball is natural agate, take absolute ethyl alcohol as ball-milling medium, and abrading-ball and composite material weight ratio are 8: 1.
3) in step 2) obtain in composite material and add 75% ethanol (V/V); wherein the ratio of composite material and 75% ethanol is 1 gram: 1.5 milliliters; stir and make mixture; then the ratio that is 10: 1 according to mixture and PVP K-30 weight ratio adds PVP K-30 as coalescents; stirring makes slurry; coat on round copper sheet; then under 60 ℃, place 15 hours; carry out annealing in process; after water cooling, dry cutting under 100 ℃; finally 600 ℃ of sintering 4 hours under argon shield atmosphere, obtain negative electrode material.Wherein the condition of annealing in process is: temperature is 420 ℃, and temperature retention time is 120 seconds, and annealing atmosphere is selected the mixed atmosphere of nitrogen and krypton, and the two volume ratio is 4: 1.
Particular product performance parameters is measured:
Adopt new prestige battery test system to carry out the test of constant current charge-discharge cycle performance to material, charging and discharging currents density is 0.2mA/cm
2, voltage range is 0.01-2V (Li+/Li).
Wherein, contrasting 1 formula is: silicon carbide powder: copper powder: graphite=10: 2: 1; The formula of contrast 2 is: silicon carbide powder: aluminium powder: graphite=10: 1: 1; The formula of contrast 3 is: silicon carbide powder: copper powder=10: 2; The preparation method of above-mentioned reference product is identical with the present invention.
Analyze: the variation of micro-structural is one of principal element of the parameters raisings such as silicon alloy negative material cycle performance and efficiency for charge-discharge, product of the present invention compared with the control, cycle performance is greatly increased, reversible capacity is 834.6mAh/g first, first charge-discharge efficiency can reach 76.5%, the 10th reversible capacity is at 452.3mAh/g, and the 30th time reversible capacity can keep 104.2mAh/g, and efficiency for charge-discharge is 58.2%.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (3)
1. the preparation method of a cathode of lithium battery composite material, comprise the steps:
1) silicon carbide micro-powder, copper powder, aluminium powder, graphite powder were according to weight ratio 10: 2: 1: 1 ratio mix and blend 30 minutes;
2) ball grinder carries out vent gas, and be filled with argon gas, by step 1) mixed material that the obtains ball-milling treatment of carrying out 60 hours of packing in ball grinder makes composite material, wherein ball grinder adopts the polyurethane grinding jar, abrading-ball is natural agate, take absolute ethyl alcohol as ball-milling medium, and ball material weight ratio is 8: 1;
3) in step 2) obtain in composite material and add 75% ethanol, wherein the ratio of composite material and 75% ethanol is 1 gram: 1.5 milliliters, stir and make mixture, then the ratio that is 10: 1 according to mixture and PVP K-30 weight ratio adds PVP K-30 as coalescents, stirring makes slurry, coat on round copper sheet, then under 60 ℃, place 15 hours, carry out annealing in process, after water cooling, dry cutting under 100 ℃, finally 600 ℃ of sintering 4 hours under argon shield atmosphere, obtain;
Described silicon carbide micro-powder is prepared from accordance with the following steps: the carborundum section sand that to choose particle diameter be 3mm, deironing, de-carbon, carry out alkali cleaning, airing is also dried, and then carries out the airflow milling pulverizing, then with the dressing sieve net in different orders footpath, is sieved, obtain particle diameter at 15-16 μ m and two kinds of silicon carbide micro-powders of 29-30 μ m, finally two kinds of silicon carbide micro-powders are mixed and get final product according to the ratio of 1: 1, wherein the content of di-iron trioxide is controlled in 0.05%, and the content of carbon is controlled in 0.05%;
Described copper powder, by copper sheet ball milling 30 hours, is then crossed 200 mesh sieves and is obtained;
Described aluminium powder, by aluminium flake ball milling 12 hours, is then crossed 200 mesh sieves and is obtained;
Described graphite powder, its particle diameter is 300 orders;
Described annealing in process be: temperature is 420 ℃, and temperature retention time is 120 seconds, and annealing atmosphere is selected the mixed atmosphere of nitrogen and krypton, and the two volume ratio is 4: 1.
2. the negative electrode material prepared in accordance with the method for claim 1.
3. the application of negative electrode material claimed in claim 2 in the lithium battery preparation.
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| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
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| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
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Owner name: LINYI JINMENG SILICON CARBIDE CO., LTD. Free format text: FORMER OWNER: HU ZUNKUI Effective date: 20120628 |
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Effective date of registration: 20120628 Address after: 276700 Shandong County of Linshu province Tai'an road Linyi Jinmeng carborundum Co. Ltd. Applicant after: Linyi JinMeng Silicon Carbide Co., Ltd. Address before: 276700 Shandong County of Linshu province Tai'an road Linyi Jinmeng carborundum Co. Ltd. Applicant before: Hu Zunkui |
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Address after: 276700 middle section of Tai'an Road, Linshu County, Linyi City, Shandong Province Patentee after: SHANDONG JINMENG NEW MATERIAL Co.,Ltd. Address before: 276700 Linyi Jinmeng silicon carbide Co., Ltd Patentee before: LINYI JINMENG SILICON CARBIDE Co.,Ltd. |
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