CN102664261B - A kind of preparation method of high-conductivity lithium ion battery cathode material - Google Patents
A kind of preparation method of high-conductivity lithium ion battery cathode material Download PDFInfo
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Abstract
The preparation method that the present invention relates to a kind of high-conductivity lithium ion battery cathode material, it is characterized in that preparation method, soluble phosphate, Fe salt are dissolved in deionized water according to mol ratio Li:Fe=1:1, utilize the silver mirror reaction principle of glucose, prepare the ferrousphosphate lithium material with surface silver cladding, glucose had both played the effect of carbon source in course of reaction, also it is the important source material of silver mirror reaction simultaneously, the electrical conductivity of material is higher, it is appreciated that in the high rate performance and the cyclical stability that improve ferrousphosphate lithium material。
Description
Technical field
The preparation method that the present invention relates to a kind of high-conductivity lithium ion battery cathode material, belongs to anode material for lithium-ion batteries technical field。
Background technology
The performance of lithium ion battery depends greatly on positive electrode used, and positive electrode chooses whether appropriately to directly affect the indices of lithium ion battery。Conventional lithium ion battery positive electrode is mainly transition metal oxide material, and owing to transition metal oxide exists mixed valence state, therefore they all have more satisfactory electronic conductivity。At present, study more transition metal oxide positive electrode and mainly include LiCoO2、LiNiO2、LiNi1/3Co1/3Mn1/3O2And LiMn2O4Etc. several。
In recent years, a class has the positive electrode of polyanionic structure and causes people's extensive concern。Wherein, LiFePO 4 (LiFePO4) it is the positive electrodes with polyanionic structure known the earliest of people, showing great attention to of people is caused, it is believed that be current optimal power lithium-ion battery positive electrode because it has stable structure, higher specific capacity, cheap price and the advantage such as environmentally friendly。At LiFePO4In material structure, bigger phosphate anion instead of the oxonium ion in INVENTIONConventional metal-oxide type positive electrode, improves LiFePO on the one hand4The structural stability of material, and then improve the cyclical stability of material。But, still further aspect but adds the distance between metallic iron ion, reduces LiFePO4Electronic conductivity。
At present, for LiFePO4The problem that electrical conductivity is relatively low, researcher is mainly through carrying out material with carbon-coated surface to it and preparing composite and solve。The preparation method that patent CN102088079, CN102013478 etc. disclose a kind of carbon cladded ferrous lithium phosphate, although carbon cladding can improve the electrical conductivity of LiFePO 4 to a certain extent, but also reduce the tap density of this material simultaneously, and then have influence on its energy density；Patent CN101891179 and CN102034980 discloses a kind of metal simple-substance aluminium powder method to prepare lithium ferrous phosphate composite material, but this procedure is complex, and electrical conductivity improves limited；Patent CN101339988 discloses a kind of preparation method at LiFePO 4 Surface coating copper, but owing to anodic potentials is higher, causes that copper easily aoxidizes, and is not suitable for business-like application。
In consideration of it, this patent by simple preparation technology, will utilize glucose silver mirror reaction principle, prepare silver cladded ferrous lithium phosphate positive electrode。Patent searching, but without finding to be prepared the Patents of silver cladded ferrous lithium phosphate material by the former lithium of silver mirror reaction。
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of high-conductivity lithium ion battery cathode material, it utilizes the silver mirror reaction principle of glucose, prepare the ferrousphosphate lithium material with surface silver cladding, glucose had both played the effect of carbon source in course of reaction, also it is the important source material of silver mirror reaction simultaneously, the electrical conductivity of material is higher, it is appreciated that in the high rate performance and the cyclical stability that improve ferrousphosphate lithium material。
The technical scheme is that and be achieved in that: the preparation method of a kind of high-conductivity lithium ion battery cathode material, it is characterised in that preparation method, specifically comprise the following steps that
A) being dissolved in deionized water by soluble phosphate, Fe salt according to mol ratio Li:Fe=1:1, be configured to solution A, solution A concentration is 3 ~ 6mol/L；
B) silver nitrate solution of 4 ~ 5% concentration is instilled in the ammonia spirit of 15 ~ 35% concentration, form silver ammino solution, hereon referred to as B solution；
C) solution A is slowly dropped in B solution, regulates pH range to 9 ~ 9.7, form C solution；Described Fe salt is Fe:Ag=(20 ~ 76 with the silver-colored mol ratio in described silver nitrate solution): 1；
D) being slowly dropped in C solution by the glucose solution of concentration 21.5 ~ 35%, glucose is (1 ~ 1.5) with the silver-colored molar ratio range in silver nitrate solution described in step b): 1, then 80 ~ 90oMagnetic agitation is carried out, until forming precursor at the temperature of C；
E) being put into by precursor and be connected with in the tube furnace of inert gas shielding and carry out pretreatment sintering, pretreatment temperature scope is 300 ~ 450oC, pretreatment time is 3 ~ 4 hours, obtains pretreatment powder；
F) above-mentioned pretreatment powder is again sintered in the tube furnace be connected with inert gas shielding, controls heating rate 10 ~ 15oC/min, sintering temperature 700 ~ 800oC, sintering time 6 ~ 10 hours, cooling method are furnace cooling, can obtain silver cladded ferrous lithium phosphate material；
Described phosphate is lithium dihydrogen phosphate；
Described Fe salt includes ferric nitrate, ferric acetate and ferric oxalate；
Described noble gas includes the mixing gas of argon, nitrogen or two kinds。
The method have the advantages that the silver mirror reaction principle utilizing glucose, prepare the ferrousphosphate lithium material with surface silver cladding, this material electric conductivity is higher, and silver exists with metallic forms, and is evenly distributed；Glucose had both played the effect of carbon source in course of reaction, was also the important source material of silver mirror reaction simultaneously；Adopt the LiFePO 4 good rate capability of this method synthesis, cycle performance excellent。
Accompanying drawing explanation
Fig. 1 is the charging and discharging curve collection of illustrative plates of 3.3wt% silver cladded ferrous lithium phosphate material in present example 1；。
Fig. 2 is the cycle performance collection of illustrative plates of 1.3wt% silver cladded ferrous lithium phosphate material in present example 2。
Fig. 3 is the XRD figure spectrum of 0.9wt% silver cladded ferrous lithium phosphate material in present example 3。
Fig. 4 is the SEM collection of illustrative plates of 0.9wt% silver cladded ferrous lithium phosphate material in present example 3。
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described with embodiment:
Embodiment 1
The ratio of lithium dihydrogen phosphate and ferric nitrate Li:Fe=1:1 in molar ratio is dissolved in appropriate deionized water, is configured to the solution that concentration is 3mol/L；The silver nitrate solution that concentration is 5% is instilled in the ammonia spirit that concentration is 20%, forms silver ammino solution；Above-mentioned 3mol/L solution is slowly dropped in silver ammino solution according to the ratio of Fe:Ag=20:1, then passes through ammonia and the pH value of solution is adjusted to 9.5；The glucose solution that concentration is 30% is slowly dropped into the solution that above-mentioned pH value is 9.5, and controlling glucose with silver-colored mol ratio is 1:1, then 80oCarry out magnetic agitation under C, form precursor；After being undertaken precursor simply grinding, putting into be connected with in the tube furnace of argon shield and be sintered, sintering temperature is 300oC, sintering time is 4 hours, obtains pretreatment powder；Being sintered in the tube furnace be connected with argon shield by pretreatment powder, sintering temperature is 700 againoC(heating rate 10oC/min), sintering time is 10 hours, adopts the mode of furnace cooling to lower the temperature, can obtain 3.3wt% silver cladded ferrous lithium phosphate material。Fig. 1 is that this material is interval at 2.7 ~ 4.2V, the charging and discharging curve of half-cell under 2C multiplying power。The initial charge capacity of material is 119mAhg-1, discharge capacity is 116mAhg-1, efficiency for charge-discharge is higher, and high rate performance is better。
Embodiment 2
The ratio of lithium dihydrogen phosphate and ferric acetate Li:Fe=1:1 in molar ratio is dissolved in appropriate deionized water, is configured to the solution that concentration is 3.5mol/L；The silver nitrate solution that concentration is 4% is instilled in the ammonia spirit that concentration is 15%, forms silver ammino solution；Above-mentioned 3.5mol/L solution is slowly dropped in silver ammino solution according to the ratio of Fe:Ag=50:1, then passes through ammonia and the pH value of solution is adjusted to 9；Being slowly dropped in the solution that above-mentioned pH value is 9 by the glucose solution that concentration is 35%, controlling glucose with silver-colored mol ratio is 1.2:1, then 85oCarry out magnetic agitation under C, form precursor；After being ground by precursor, putting into be connected with in the tube furnace of argon shield and be sintered, sintering temperature is 350oC, sintering time is 3 hours, obtains pretreatment powder；Being sintered in the tube furnace be connected with nitrogen protection by pretreatment powder, sintering temperature is 800 againoC(heating rate 15oC/min), sintering time is 6 hours, adopts the mode of furnace cooling to lower the temperature, can obtain 1.3wt% silver cladded ferrous lithium phosphate material。Fig. 2 is that this material is interval at 2.7 ~ 4.2V, the cycle performance curve of half-cell under 1C multiplying power。Can be seen that material discharge capacity first is 146mAhg-1, after 30 circulations, capacity remains to be maintained at 144mAhg-1, capability retention 99%, cycle performance is better。
Embodiment 3
The ratio of lithium dihydrogen phosphate and ferric nitrate Li:Fe=1:1 in molar ratio is dissolved in deionized water, is configured to the solution that concentration is 6mol/L；The silver nitrate solution that concentration is 4.5% is instilled in the ammonia spirit that concentration is 35%, forms silver ammino solution；Above-mentioned 4.5mol/L solution is instilled in silver ammino solution according to the ratio of Fe:Ag=76:1, then passes through ammonia and the pH value of solution is adjusted to 9.7；Being slowly dropped in the solution that above-mentioned pH value is 9.7 by the glucose solution that concentration is 21.5%, controlling glucose with silver-colored mol ratio is 1.5:1, then 90oIt is stirred under C, forms precursor；After being ground by precursor, putting into and be connected with argon and nitrogen (volume ratio is 1:1) mixes in the tube furnace of gas and is sintered, sintering temperature is 320oC, sintering time is 4 hours, obtains pretreatment powder；Being sintered in the tube furnace be connected with argon shield by pretreatment powder, sintering temperature is 720oC(heating rate 12oC/min), sintering time is 7 hours, adopts the mode of furnace cooling to lower the temperature, can obtain 0.9wt% silver cladded ferrous lithium phosphate material。Fig. 3 is that material is 10 ~ 60oXRD figure spectrum in scope, as can be seen from the figure material and the XRD figure of pure phase ferrousphosphate lithium material are composed consistent, it does not have the reason seeing metal Ag diffraction maximum is owing to the content of metal Ag is less。Fig. 4 is that this material is in the scanning electron microscope diagram spectrum that amplification is when 5000。
Embodiment 4
The ratio of lithium dihydrogen phosphate and ferric oxalate Li:Fe=1:1 in molar ratio is dissolved in appropriate deionized water, is configured to the solution that concentration is 3mol/L；The silver nitrate solution that concentration is 5% is instilled in the ammonia spirit that concentration is 20%, forms silver ammino solution；Above-mentioned 3mol/L solution is slowly dropped in silver ammino solution according to the ratio of Fe:Ag=20:1, then passes through ammonia and the pH value of solution is adjusted to 9.5；The glucose solution that concentration is 30% is slowly dropped into the solution that above-mentioned pH value is 9.5, and controlling glucose with silver-colored mol ratio is 1:1, then 80oCarry out magnetic agitation under C, form precursor；After being undertaken precursor simply grinding, putting into be connected with in the tube furnace of argon shield and be sintered, sintering temperature is 300oC, sintering time is 4 hours, obtains pretreatment powder；Being sintered in the tube furnace be connected with argon shield by pretreatment powder, sintering temperature is 700 againoC(heating rate 10oC/min), sintering time is 10 hours, adopts the mode of furnace cooling to lower the temperature, can obtain 3.3wt% silver cladded ferrous lithium phosphate material。
Claims (3)
1. the preparation method of a high-conductivity lithium ion battery cathode material, it is characterised in that preparation method, specifically comprises the following steps that
A) being dissolved in deionized water by soluble phosphate and lithium dihydrogen phosphate, Fe salt according to mol ratio Li:Fe=1:1, be configured to solution A, solution A concentration is 3 ~ 6mol/L；
B) silver nitrate solution of 4 ~ 5% concentration is instilled in the ammonia spirit of 15 ~ 35% concentration, form silver ammino solution, hereon referred to as B solution；
C) solution A is slowly dropped in B solution, regulates pH value range to 9 ~ 9.7, form C solution；Described Fe salt is Fe:Ag=(20 ~ 76 with the silver-colored mol ratio in described silver nitrate solution): 1；
D) being slowly dropped in C solution by the glucose solution of concentration 21.5 ~ 35%, glucose is (1 ~ 1.5) with the silver-colored molar ratio range in silver nitrate solution described in step b): 1, then 80 ~ 90oMagnetic agitation is carried out, until forming precursor at the temperature of C；
E) being put into by precursor and be connected with in the tube furnace of inert gas shielding and carry out pretreatment sintering, pretreatment temperature scope is 300 ~ 450oC, pretreatment time is 3 ~ 4 hours, obtains pretreatment powder；
F) above-mentioned pretreatment powder is again sintered in the tube furnace be connected with inert gas shielding, controls heating rate 10 ~ 15oC/min, sintering temperature 700 ~ 800oC, sintering time 6 ~ 10 hours, cooling method are furnace cooling, can obtain silver cladded ferrous lithium phosphate material。
2. the preparation method of a kind of high-conductivity lithium ion battery cathode material according to claim 1, it is characterised in that described Fe salt includes ferric nitrate, ferric acetate or ferric oxalate。
3. the preparation method of a kind of high-conductivity lithium ion battery cathode material according to claim 1, it is characterised in that described noble gas includes the mixing gas of argon, nitrogen or two kinds。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103413942B (en) * | 2013-07-30 | 2015-08-12 | 中国第一汽车股份有限公司 | A kind of method for preparing anode material of lithium-ion battery |
| CN107093710B (en) * | 2017-03-31 | 2019-10-08 | 宁夏博尔特科技有限公司 | Two-coat lithium ion battery negative material and preparation method thereof and lithium ion battery |
| CN107359343B (en) * | 2017-07-28 | 2020-06-19 | 南京理工大学 | Preparation method of spiral-like silver nanochain conductor bridged modified lithium iron phosphate composite material |
| CN108270005B (en) * | 2018-01-19 | 2020-06-09 | 河北力滔电池材料有限公司 | Lithium iron phosphate composite positive pole piece and preparation method thereof |
| CN108390054A (en) * | 2018-03-07 | 2018-08-10 | 南京理工大学 | The preparation method of four-prism shape LiFePO4/silver/graphene oxide ternary composite electrode material |
| CN108539179B (en) * | 2018-04-28 | 2020-11-20 | 河南工业大学 | Lithium vanadium phosphate composite electrode material and preparation method and application thereof |
| CN112038629B (en) * | 2020-09-30 | 2022-07-05 | 合肥国轩高科动力能源有限公司 | Integrated high-rate lithium iron phosphate positive electrode material and preparation method and application thereof |
| CN113130891A (en) * | 2021-04-16 | 2021-07-16 | 中国工程物理研究院电子工程研究所 | Thermal battery composite cathode material and preparation method thereof |
| CN115775883B (en) * | 2023-02-13 | 2023-06-02 | 四川富临新能源科技有限公司 | Surface modification method of lithium iron phosphate positive electrode material |
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| CN101000956A (en) * | 2006-12-29 | 2007-07-18 | 中国科学院上海硅酸盐研究所 | Silver electrode composite material of lithium secondary battery and low temp. preparation method thereof |
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| CN101000956A (en) * | 2006-12-29 | 2007-07-18 | 中国科学院上海硅酸盐研究所 | Silver electrode composite material of lithium secondary battery and low temp. preparation method thereof |
| CN101621122A (en) * | 2009-08-07 | 2010-01-06 | 珠海市鹏辉电池有限公司 | Preparation method of lithium iron phosphate compound material |
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