CN103833044B - A kind of preparation method of anode material for lithium-ion batteries manganese borate lithium - Google Patents
A kind of preparation method of anode material for lithium-ion batteries manganese borate lithium Download PDFInfo
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Abstract
A preparation method for anode material for lithium-ion batteries manganese borate lithium, comprises the following steps: lithium metaborate, lithium acetate, manganese acetate and glucose are dissolved in deionized water by (1), stir; (2) put pre-freeze in cold-trap into, after pre-freeze, take out from cold-trap, put drying frame into, be put into by drying frame above cold-trap, in cold-trap, temperature is set as-50 ~-20 DEG C, starts vacuum pump, does is vacuum degree set to below 15Pa, dry 20-24? h; (3) under argon shield with the ramp of 1 ~ 5 DEG C per minute to 350 ~ 450 DEG C, constant temperature 4 ~ 6h, then with ramp to 600 ~ 700 DEG C of 1 ~ 5 DEG C per minute, constant temperature 4 ~ 6h, passes into argon gas, naturally cools to room temperature.The present invention is simple to operate, favorable reproducibility, and presoma material particular diameter is tiny, and sintering gained material particular diameter can control very well, and carbon covered effect is better, and have good electronic conductivity, first charge-discharge specific capacity is high.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, particularly relate to a kind of freeze drying-solid-phase sintering preparation method of anode material for lithium-ion batteries manganese borate lithium.
Background technology
Along with becoming increasingly conspicuous and the high speed development of modern science and technology of energy and environment problem, the performance of people to battery is had higher requirement.The advantages such as operating voltage is high owing to having for lithium ion battery, energy density is large, have extended cycle life and self discharge is little, are widely used in the fields such as portable electric appts, electric tool, space technology and national defense industry.In recent years, a new generation's electronic product and the development & application of electric automobile propose requirements at the higher level to the energy density of secondpower supply system and power density, and the Design & preparation of novel high-capacity electrode material particularly positive electrode is the key obtaining high performance lithium ion battery.The polyanionic compound of many research groups report has good performance as anode material for lithium-ion batteries, very likely becomes positive electrode of new generation.
In many polyanionic compounds of current research and development, phosphate cathode material is the focus of research and development, but compared with borate, the specific discharge capacity of phosphate cathode material is lower, as lithium manganese phosphate (LiMnPO
4) Theoretical Mass specific capacity only have 171mAh/g, this can not meet the demand of society to high-capacity battery material very well, by contrast, manganese borate lithium (LiMnBO
3) be a kind of novel polyanionic positive electrode, because borate (BO
3 3-) molal weight only have 58.8g/mol, be less than phosphate radical (PO
4 3-) 95.0g/mol, instead of phosphate radical with lighter borate in the structure, make manganese borate lithium have higher capacity, its Theoretical Mass specific capacity can reach 222mAh/g.Simultaneously, boron atom has the oxytropism of height, form ring-type, caged with oxygen atom and be then polymerized chaining, sheet, netted again, the diversity of this structure will bring diversified performance, as nonlinear optics, ferroelectric, the characteristic such as piezoelectricity and semiconductor behavior and cause the extensive concern of material science.LiMnBO is made just because of various structural advantage
3there is good invertibity, excellent chemistry and electrochemical stability, therefore, LiMnBO
3it is a kind of anode material for lithium-ion batteries having very much DEVELOPMENT PROSPECT.
The preparation method of existing anode material for lithium-ion batteries manganese borate lithium mainly contains spray drying process, mechanical attrition method, sol-gal process, hydro thermal method etc.
Spray drying process is by liquid phase dissolved Direct spraying, if solubility is very large, owing to there is no nucleation core, target product can not be collected, if solubility is less, joining fail to dissolve completely in solution, woven hose is easily caused to block, spraying gained material skewness, and then causing sintering resulting materials dephasign a lot, chemical property is poor, carries out first charge-discharge circulation with 1/40C multiplying power in 1.0-4.8V potential region, can obtain initial charge specific capacity is 60.7mAh/g, and specific discharge capacity is 43.3mAh/g.
Mechanical attrition method noise is large, and resulting materials purity is not high, and particle is larger and uneven, and degree of crystallinity is low, and the method is difficult to the defects such as electronics and ionic conductivity by improving material existence itself is low to improve the overall chemical property of material.
Sol-gal process and hydro thermal method long for experimental period, reappearance is poor, and condition is difficult to control, and raw material is selected harsh, seriously constrains it and uses and promote.
Summary of the invention
Technical problem to be solved by this invention is, a kind of raw material is provided to be easy to get, simple to operate, reappearance is high, and controllability is good, environmental friendliness, the particle diameter of obtained anode material for lithium-ion batteries manganese borate lithium is tiny, and be evenly distributed, degree of crystallinity is high, electronic conductivity is high, the preparation method of the anode material for lithium-ion batteries manganese borate lithium that chemical property is good.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of anode material for lithium-ion batteries manganese borate lithium, comprises the following steps:
(1) lithium metaborate, lithium acetate, manganese acetate and glucose are dissolved in deionized water, stir, obtain gelatinous mixture;
The mol ratio of described lithium metaborate, lithium acetate, manganese acetate and glucose is 1:0.03:1:0.20-0.75;
(2) gelatinous mixture of step (1) gained is placed on pre-freeze frame, put pre-freeze 5 ~ 10h in cold-trap together into, pre-freezing temperature is set as-50 ~-20 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-50 ~-20 DEG C, start vacuum pump, vacuum degree is set to below 15Pa, after dry 20-24h, open vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma,
(3) by the presoma of step (2) gained under the argon shield of purity >=99.999%; with the ramp of 1 ~ 5 DEG C per minute to 350 ~ 450 DEG C; constant temperature 4 ~ 6h; again with ramp to 600 ~ 700 DEG C of 1 ~ 5 DEG C per minute; constant temperature 4 ~ 6h; then continue the argon gas passing into purity >=99.999%, naturally cool to room temperature.
Further, in step (1), the total mass ratio of the volume of deionized water used and lithium metaborate, lithium acetate, manganese acetate and glucose four kinds of materials is 3.0-6.0:1.0, and unit is ml/g or L/kg.
Further, in step (1), the reproducibility carbon sources such as available oxalic acid, tartaric acid or citric acid substitute glucose.
The present invention is after the various method of comprehensive analysis, uses Vacuum Freezing & Drying Technology, i.e. lyophilization technology, aqueous mixture is freezed in advance, then make its moisture distil under vacuum and low-temperature condition, reach and simplify the operation, the tiny and uniform object of obtained granular precursor.
The present invention utilizes freeze drying-solid sintering technology to prepare submicron order pure phase manganese borate lithium, and for preparation, also improving manganese borate lithium properties further provides new way.
The present invention adopts freeze drying-solid sintering technology, simple to operate, favorable reproducibility, presoma material particular diameter is tiny, sintering gained material particular diameter also can control very well, carbon covered effect is better, and have good electronic conductivity, first charge-discharge specific capacity is high, good cycle, with 1/40C multiplying power in 1.0-4.8V potential region, initial charge specific capacity is 212.6mAh/g, and specific discharge capacity is 209.3mAh/g.
Compared with prior art, the present invention has the following advantages:
(1) raw material sources are extensive, and environmental friendliness, controllability is good;
(2) experimental implementation is simple, and reappearance is high;
(3) particle diameter of the manganese borate lithium that obtained uniform carbon is coated is in sub-micron rank, and good dispersion, the degree of crystallinity of particle are high, and material is pure phase free from admixture, and have higher reversible first charging and discharging capacity, chemical property has clear improvement.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction figure of the coated nanoscale manganese borate lithium of the uniform carbon of embodiment 1 gained;
Fig. 2 is the scanning electron microscope diagram of the coated nanoscale manganese borate lithium of the uniform carbon of embodiment 1 gained;
Fig. 3 is the first charge-discharge curve chart of the coated nanoscale manganese borate lithium of the uniform carbon of embodiment 1 gained.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
Get 4.99g lithium metaborate, 0.20g lithium acetate, 17.31g manganese acetate, 3.60g glucose, be dissolved in 150ml deionized water, magnetic agitation 5h in beaker, obtains gelatinous mixture; Gained gelatinous mixture is placed on pre-freeze frame, put pre-freeze 5h in cold-trap together into, pre-freezing temperature is set as-50 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-50 DEG C, and start vacuum pump, vacuum degree is set to below 15Pa, after dry 24h, open vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma; By gained presoma under purity 99.999% argon shield, with the ramp of 5 DEG C per minute to 400 DEG C, constant temperature 5h; and then be warmed up to 600 DEG C with the speed of 5 DEG C per minute, constant temperature 5h, finally continue the argon gas passing into purity 99.999%; naturally cool to room temperature.
As shown in Figure 1, X-ray powder diffraction analysis shows that the product of gained is LiMnBO
3, do not have other dephasigns, degree of crystallinity is high.
As shown in Figure 2, be the composite material of the coated manganese borate lithium of in-situ carbon from the known products therefrom of scanning electron microscope analysis, wherein LiMnBO
3particle diameter be about 100nm.
As shown in Figure 3, using the product of gained as positive pole, metal lithium sheet is as negative pole, be full of argon gas, water oxygen is all assembled into experiment fastening lithium ionic cell lower than in the glove box of 0.1ppm, carries out first charge-discharge circulation with 1/40C multiplying power in 1.0 ~ 4.8V potential region, and can obtain initial charge specific capacity is 212.6mAh/g, specific discharge capacity is 209.3mAh/g, shows good chemical property.
Embodiment 2
Get 4.99g lithium metaborate, 0.20g lithium acetate, 17.31g manganese acetate, 13.50g glucose, be dissolved in 200ml deionized water, magnetic agitation 5h in beaker, obtains gelatinous mixture; Gained gelatinous mixture is placed on pre-freeze frame, put pre-freeze 7h in cold-trap together into, pre-freezing temperature is set as-30 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-40 DEG C, and start vacuum pump, vacuum degree is set to below 15Pa, after dry 23h, open vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma; By gained presoma under the argon shield of purity 99.999%, with the ramp of 5 DEG C per minute to 400 DEG C, constant temperature 5h; and then be warmed up to 600 DEG C with the speed of 5 DEG C per minute, constant temperature 5h, finally continue the argon gas passing into purity 99.999%; naturally cool to room temperature.
Using the product of gained as positive pole, metal lithium sheet is as negative pole, be full of argon gas, water oxygen is all assembled into experiment fastening lithium ionic cell lower than in the glove box of 0.1ppm, in 1.0 ~ 4.8V potential region, first charge-discharge circulation is carried out with 1/40C multiplying power, can obtain initial charge specific capacity is 183.2mAh/g, and specific discharge capacity is 172.4mAh/g, shows good chemical property.
Embodiment 3
Get 4.99g lithium metaborate, 0.20g lithium acetate, 17.31g manganese acetate, 13.50g glucose, be dissolved in 200ml deionized water, magnetic agitation 5h in beaker, obtains gelatinous mixture; Gained gelatinous mixture is placed on pre-freeze frame, put pre-freeze 6h in cold-trap together into, pre-freezing temperature is set as-40 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-30 DEG C, and start vacuum pump, vacuum degree is set to below 15Pa, after dry 24h, after opening vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma; By gained presoma under the argon shield of purity 99.999%, with the ramp of 5 DEG C per minute to 400 DEG C, constant temperature 5h; and then be warmed up to 700 DEG C with the speed of 5 DEG C per minute, constant temperature 5h, finally continue the argon gas passing into purity 99.999%; naturally cool to room temperature.
Using the product of gained as positive pole, metal lithium sheet is as negative pole, be full of argon gas, water oxygen is all assembled into experiment fastening lithium ionic cell lower than in the glove box of 0.1ppm, in 1.0 ~ 4.8V potential region, first charge-discharge circulation is carried out with 1/40C multiplying power, can obtain initial charge specific capacity is 173.7mAh/g, and specific discharge capacity is 168.5mAh/g, shows good chemical property.
Embodiment 4
Get 4.99g lithium metaborate, 0.20g lithium acetate, 17.31g manganese acetate, 3.60g glucose, be dissolved in 150ml deionized water, magnetic agitation 5h in beaker, obtains gelatinous mixture; Gained gelatinous mixture is placed on pre-freeze frame, put pre-freeze 5h in cold-trap together into, pre-freezing temperature is set as-50 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-40 DEG C, and start vacuum pump, vacuum degree is set to below 15Pa, after dry 22h, after opening vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma; By gained presoma under the argon shield of purity 99.999%, with the ramp of 5 DEG C per minute to 400 DEG C, constant temperature 5h; and then be warmed up to 700 DEG C with the speed of 5 DEG C per minute, constant temperature 5h, finally continue the argon gas passing into purity 99.999%; naturally cool to room temperature.
Using the product of gained as positive pole, metal lithium sheet is as negative pole, be full of argon gas, water oxygen is all assembled into experiment fastening lithium ionic cell lower than in the glove box of 0.1ppm, in 1.0 ~ 4.8V potential region, first charge-discharge circulation is carried out with 1/40C multiplying power, can obtain initial charge specific capacity is 176.9mAh/g, and specific discharge capacity is 165.8mAh/g, shows good chemical property.
Embodiment 5
Get 4.99g lithium metaborate, 0.20g lithium acetate, 17.31g manganese acetate, 1.80g oxalic acid, be dissolved in 150ml deionized water, in beaker, magnetic agitation 5 hours, obtains gelatinous mixture; Gained gelatinous mixture is placed on pre-freeze frame, put pre-freeze 5h in cold-trap together into, pre-freezing temperature is set as-50 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-50 DEG C, and start vacuum pump, vacuum degree is set to below 15Pa, after dry 24h, after opening vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma; By gained presoma under the argon shield of purity 99.999%, with the ramp of 5 DEG C per minute to 400 DEG C, constant temperature 5h; and then be warmed up to 650 DEG C with the speed of 5 DEG C per minute, constant temperature 5h, finally continue the argon gas passing into purity 99.999%; naturally cool to room temperature.
Using the product of gained as positive pole, metal lithium sheet is as negative pole, be full of argon gas, water oxygen is all assembled into experiment fastening lithium ionic cell lower than in the glove box of 0.1ppm, in 1.0 ~ 4.8V potential region, first charge-discharge circulation is carried out with 1/40C multiplying power, can obtain initial charge specific capacity is 183.2mAh/g, and specific discharge capacity is 175.8mAh/g, shows good chemical property.
Embodiment 6
Get 4.99g lithium metaborate, 0.20g lithium acetate, 17.31g manganese acetate, 6.75g oxalic acid, be dissolved in 150ml deionized water, in beaker, magnetic agitation 5 hours, obtains gelatinous mixture; Gained gelatinous mixture is placed on pre-freeze frame, put pre-freeze 6h in cold-trap together into, pre-freezing temperature is set as-40 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-40 DEG C, and start vacuum pump, vacuum degree is set to below 15Pa, after dry 24h, after opening vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma; By gained presoma under the argon shield of purity 99.999%, with the ramp of 5 DEG C per minute to 400 DEG C, constant temperature 5h; and then be warmed up to 700 DEG C with the speed of 5 DEG C per minute, constant temperature 5h, finally continue the argon gas passing into purity 99.999%; naturally cool to room temperature.
Using the product of gained as positive pole, metal lithium sheet is as negative pole, be full of argon gas, water oxygen is all assembled into experiment fastening lithium ionic cell lower than in the glove box of 0.1ppm, in 1.0 ~ 4.8V potential region, first charge-discharge circulation is carried out with 1/40C multiplying power, can obtain initial charge specific capacity is 186.7mAh/g, and specific discharge capacity is 169.1mAh/g, shows good chemical property.
Claims (3)
1. a preparation method for anode material for lithium-ion batteries manganese borate lithium, is characterized in that, comprises the following steps:
(1) lithium metaborate, lithium acetate, manganese acetate and glucose are dissolved in deionized water, stir, obtain gelatinous mixture;
The mol ratio of described lithium metaborate, lithium acetate, manganese acetate and glucose is 1:0.03:1:0.20-0.75;
(2) gelatinous mixture of step (1) gained is placed on pre-freeze frame, put pre-freeze 5 ~ 10h in cold-trap together into, pre-freezing temperature is set as-50 ~-20 DEG C, after pre-freeze, the material disc that pre-freeze is good takes out from cold-trap, put drying frame into, drying frame is put into above cold-trap, plexiglass tent on cover, cover lower end contacts completely with " O " RunddichtringO, in cold-trap, temperature is set as-50 ~-20 DEG C, start vacuum pump, vacuum degree is set to below 15Pa, after dry 20-24h, open vacuum valve inflation, stop the work of vacuum pump and compressor successively, obtain presoma,
(3) by the presoma of step (2) gained under the argon shield of purity >=99.999%; with the ramp of 1 ~ 5 DEG C per minute to 350 ~ 450 DEG C; constant temperature 4 ~ 6h; again with ramp to 600 ~ 700 DEG C of 1 ~ 5 DEG C per minute; constant temperature 4 ~ 6h; then continue the argon gas passing into purity >=99.999%, naturally cool to room temperature.
2. the preparation method of anode material for lithium-ion batteries manganese borate lithium according to claim 1, it is characterized in that: in step (1), the total mass ratio of the volume of deionized water used and lithium metaborate, lithium acetate, manganese acetate and glucose four kinds of materials is 3.0-6.0:1.0, and unit is ml/g or L/kg.
3. the preparation method of anode material for lithium-ion batteries manganese borate lithium according to claim 1 and 2, is characterized in that: in step (1), substitute glucose with oxalic acid, tartaric acid or citric acid.
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| CN104064773A (en) * | 2014-07-07 | 2014-09-24 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of carbon-coated lithium manganese borate cathode material for lithium ion battery |
| CN104821390B (en) * | 2015-04-24 | 2017-08-25 | 中南大学 | A kind of anode material for lithium-ion batteries manganese borate lithium/graphene and preparation method thereof |
| CN105129758B (en) * | 2015-06-30 | 2017-12-19 | 中南大学 | A kind of porous calcium phosphate manganese vanadium lithium composite positive pole and preparation method thereof |
| CN110828823A (en) * | 2019-11-19 | 2020-02-21 | 湖北理工学院 | Preparation method of lithium manganese borate/carbon composite material |
| CN111509206A (en) * | 2020-04-23 | 2020-08-07 | 中国科学院过程工程研究所 | Composite lithium-rich cathode material and preparation method and application thereof |
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| CN101475158A (en) * | 2009-01-09 | 2009-07-08 | 北京工业大学 | Preparation of lithium ionic cell anode material LiFeO4 |
| CN102403505A (en) * | 2011-12-15 | 2012-04-04 | 山东大学 | Method for preparing lithium ion battery cathode material in-situ carbon coated lithium manganese borate composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101475158A (en) * | 2009-01-09 | 2009-07-08 | 北京工业大学 | Preparation of lithium ionic cell anode material LiFeO4 |
| CN102403505A (en) * | 2011-12-15 | 2012-04-04 | 山东大学 | Method for preparing lithium ion battery cathode material in-situ carbon coated lithium manganese borate composite material |
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| Title |
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