CN102709561A - Preparation method of carbon nano-Li2FeSiO4 composite cathode material - Google Patents

Preparation method of carbon nano-Li2FeSiO4 composite cathode material Download PDF

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CN102709561A
CN102709561A CN2012102037976A CN201210203797A CN102709561A CN 102709561 A CN102709561 A CN 102709561A CN 2012102037976 A CN2012102037976 A CN 2012102037976A CN 201210203797 A CN201210203797 A CN 201210203797A CN 102709561 A CN102709561 A CN 102709561A
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lithium
preparation
carbon
carbon nano
positive pole
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官轮辉
赵毅
李加新
许交兴
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention provides a preparation method of a carbon nano-Li2FeSiO4 composite cathode material. The preparation method comprises the following steps of: uniformly loading different contents of silica on the surface of a carbon nanomaterial, taking a carbon nano-silica compound as a template, dissolving the carbon nano-silica compound in ethanol according to the molar ratio of Fe element to Si element to Li element of 1: 1: 2 and carrying out uniform ultrasonic mixing; stirring the mixing liquid at 60 DEG C till the ethanol is completely volatilized, uniformly grinding the obtained solid in an agate mortar, and tabletting the powder obtained after grinding; and heating the tablets in an inert atmosphere to 550-650 DEG C and calcining at constant temperature for 5-10h to obtain the carbon nano-Li2FeSiO4 composite cathode material with a core-shell structure.

Description

The preparation method of carbon nanometer-ferrosilicon silicate of lithium composite positive pole
Technical field
The present invention relates to a kind of preparation method of carbon nanometer-ferrosilicon silicate of lithium composite positive pole of nucleocapsid structure, belong to the energy and material preparing technical field.
Background technology
New type lithium ion positive electrode Li 2FeSiO 4, because its theoretical specific capacity is high, cheap, environmental friendliness, advantage such as fail safe is good has caused people's extensive concern since 2005 report, be considered to have the anode material for lithium-ion batteries of future generation of potentiality.Theoretically, 1mol Li 2FeSiO 4Can take off embedding 2mol lithium ion, its theoretical capacity is up to 332mAh g -1, far above present commercial LiFePO 4(170 mAh g -1).Yet, Li 2FeSiO 4Conductivity low, can only take off lithium ion of embedding usually, cause its capacity to be lower than 166 mAh g -1At present, the researcher mainly improves the electron conduction and the ionic conductivity of ferrosilicon silicate of lithium through the method that carbon coats, thereby promotes its chemical property.Traditional carbon coat be method through ball milling with carbon matrix precursor and raw materials mix, high-temperature calcination obtains the ferrosilicon silicate of lithium composite material that carbon coats then.For example, sucrose is mixed through ball milling with the ferrosilicon silicate of lithium presoma, in nitrogen atmosphere, calcined 10 hours for 600 ℃, preparation Li 2FeSiO 4/ C composite material, demonstrate good high rate performance (Z. L. Gong, Y. X. Li, G. N. He, J. Li and Y. Yang, Electrochemical and Solid State Letters, 2008,11, A60-A63.).Yet traditional method can not realize uniform carbon and coat, limit the further raising of ferrosilicon silicate of lithium performance.
The present invention passes through silicon dioxide carried on the carbon nanomaterial surface; And as the silicon source; Can obtain the carbon nanometer-ferrosilicon silicate of lithium composite material of nucleocapsid structure, realize the even dispersion of carbon nanomaterial in ferrosilicon silicate of lithium, effectively improve the conductivity and the chemical property of material.
Summary of the invention
The present invention adopts carbon nanometer-silicon dioxide composite material as template and silicon source, is the mixed of 1:1:2 by iron, silicon, elemental lithium mol ratio, prepares the carbon nanometer-ferrosilicon silicate of lithium composite positive pole of nucleocapsid structure through the method for solid-phase sintering.Can effectively reduce the size of ferrosilicon silicate of lithium through the composite material of this method preparation, make carbon nanomaterial be dispersed in uniformly in the composite material, effectively improve conductivity of electrolyte materials and electro-chemical activity.
Preparation method of the present invention may further comprise the steps:
(1) silicon dioxide of uniform load different content at first on carbon nanomaterial surface; With carbon nanometer-silicon dioxide compound, ferrous oxalate, Li source compound is raw material; In iron, silicon, elemental lithium mol ratio is that the ratio of 1:1:2 is dissolved in the ethanol ultrasonic mixing.
(2) mixed liquor in the step 1 stirs down at 60 ℃ and volatilizees fully up to ethanol, and the gained solid grinds in agate mortar evenly, compressing tablet.
(3) in inert atmosphere, be heated to 550-650 ℃, calcining at constant temperature 5-10 hour, make the carbon nanometer-ferrosilicon silicate of lithium composite material of nucleocapsid structure.
Described carbon nanomaterial comprises multi-walled carbon nano-tubes, SWCN, Graphene and single wall carbon nanohorn.
The percentage by weight of carbon nanomaterial in composite material is 8-20wt%, and the content of ferrosilicon silicate of lithium is 80-92wt%.
Described Li source compound is one or more in lithium acetate, lithium formate, lithium hydroxide and the lithium nitrate.
Described inert atmosphere is nitrogen or argon gas.
Advantage of the present invention: (1) adopts carbon nanometer-silicon dioxide composite material as template and silicon source, prepares the carbon nanometer-ferrosilicon silicate of lithium composite positive pole of nucleocapsid structure, effectively improves conductivity of electrolyte materials.(2) its synthesis temperature is low, and synthetic method is simple, is easy to realize industrialization.(3) ferrosilicon silicate of lithium of preparation is a nanoscale, effectively improves its electrochemistry and lives, and under the multiplying power of 1C, through 120 circulations, its capacity still remains on 180 mAh g -1, demonstrate excellent cycle performance and high rate performance.
Description of drawings
Fig. 1 is the transmission electron microscope picture of sample among the embodiment 1;
Fig. 2 is the X ray diffracting spectrum of embodiment 3 samples;
Fig. 3 is the transmission electron microscope picture of embodiment 3 samples;
Fig. 4 is the cycle performance figure of embodiment 3 samples.
Used test instrument model and producer are respectively: and transmission electron microscope (JEM-2010, JEOL), X-ray diffractometer (RIGAKU SCXmini, Rigaku), battery test system (LAND 2001A, Wuhan Jin Nuo Electronics Co., Ltd.)
Embodiment
Ultrasonic being dispersed in the red fuming nitric acid (RFNA) of embodiment 1. commercial multi-walled carbon nano-tubes under 140 ℃ of oil baths, refluxed 6 hours, used distilled water fully to wash to filtrating and was neutrality, in 80 ℃ of baking ovens, dried, and obtained the multi-walled carbon nano-tubes of acidifying.In the mixed solution of 160mL ethanol and 16mL deionized water, add the multi-walled carbon nano-tubes of different quality, be uniformly dispersed in ultrasonic one hour, under magnetic agitation, add 1.28gTEOS and 2mL ammoniacal liquor respectively, continue to stir 24 hours.Finally obtain the multi-walled carbon nano-tubes silicon dioxide composite material of different loads amount, Fig. 1 shows that dioxide-containing silica is the pattern of the composite material of 56wt%, and unbodied silicon dioxide loads on the multi-wall carbon nano-tube tube-surface uniformly, and its thickness is 10-12nm.
Embodiment 2. is that the multi-walled carbon nano-tubes silicon dioxide composite material of 76wt% is the silicon source with the dioxide-containing silica; Ferrous oxalate and lithium acetate are respectively source of iron and lithium source; In iron, silicon, elemental lithium mol ratio is that the ratio of 1:1:2 is dissolved in the 20mL ethanol; Be uniformly dispersed in ultrasonic one hour, and in 60 ℃ of oil baths, stirred and volatilize fully up to ethanol.The gained solid is ground in agate mortar evenly, compressing tablet, under argon gas atmosphere, 5 ℃/min is heated to 650 ℃, and insulation 10h obtains multi-walled carbon nano-tubes-ferrosilicon silicate of lithium composite material behind the natural cooling.
Embodiment 3. is that the multi-walled carbon nano-tubes silicon dioxide composite material of 56wt% is the silicon source with the dioxide-containing silica; Ferrous oxalate and lithium acetate are respectively source of iron and lithium source; In iron, silicon, elemental lithium mol ratio is that the ratio of 1:1:2 is dissolved in the 20mL ethanol; Be uniformly dispersed in ultrasonic one hour, and in 60 ℃ of oil baths, stirred and volatilize fully up to ethanol.The gained solid is ground in agate mortar evenly, compressing tablet, under argon gas atmosphere, 5 ℃/min is heated to 600 ℃, is incubated 5h, obtains the multi-walled carbon nano-tubes-ferrosilicon silicate of lithium composite material of nucleocapsid structure behind the natural cooling.MWNTsLi 2FeSiO 4The XRD figure spectrum of composite material is as shown in Figure 2, and wherein ferrosilicon silicate of lithium is a monocline, and space group is P2 1/ n is 26 oNear peak is the diffraction maximum of multi-walled carbon nano-tubes.Nucleocapsid structure MWNTsLi 2FeSiO 4Pattern as shown in Figure 3, ferrosilicon silicate of lithium loads on multi-wall carbon nano-tube tube-surface, Li uniformly 2FeSiO 4The thickness of layer is 20-25nm, and wherein the content of multi-walled pipes is 20wt%.Fig. 4 is MWNTsLi 2FeSiO 4Composite material is cycle performance figure under the 1C multiplying power.Under the multiplying power of 1C, after 120 circulations, the discharge capacity of ferrosilicon silicate of lithium still remains on 180 mAh g -1, demonstrate excellent cycle performance and high rate performance.

Claims (5)

1. the preparation method of carbon nanometer-ferrosilicon silicate of lithium composite positive pole may further comprise the steps:
1) silicon dioxide of uniform load different content on carbon nanomaterial surface at first is template with carbon nanometer-silicon dioxide compound, is that the ratio of 1:1:2 is dissolved in the ethanol ultrasonic mixing in iron, silicon, elemental lithium mol ratio;
2) mixed liquor in the step 1) stirs down at 60 ℃ and volatilizees fully up to ethanol, and the gained solid grinds in agate mortar evenly, compressing tablet;
3) in inert atmosphere, be heated to 550-650 ℃, calcining at constant temperature 5-10 hour, make the carbon nanometer-ferrosilicon silicate of lithium composite material of nucleocapsid structure.
2. the preparation method of composite positive pole according to claim 1, it is characterized in that: described carbon nanomaterial comprises multi-walled carbon nano-tubes, SWCN, Graphene and single wall carbon nanohorn.
3. the preparation method of composite positive pole according to claim 1, it is characterized in that: the percentage by weight of described carbon nanomaterial in composite material is 8-20wt%, the content of ferrosilicon silicate of lithium is 80-92wt%.
4. the preparation method of composite positive pole according to claim 1, it is characterized in that: described Li source compound is one or more in lithium acetate, lithium formate, lithium hydroxide and the lithium nitrate.
5. the preparation method of composite positive pole according to claim 1, it is characterized in that: the inert atmosphere in the said step 3 is nitrogen or argon gas.
CN2012102037976A 2012-06-19 2012-06-19 Preparation method of carbon nano-Li2FeSiO4 composite cathode material Pending CN102709561A (en)

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Cited By (7)

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CN102916184A (en) * 2012-10-23 2013-02-06 中国科学院过程工程研究所 Lithium silicate compound of anode material of lithium ion battery, and preparation method and application for lithium silicate compound
CN103050692A (en) * 2012-12-21 2013-04-17 中国科学院福建物质结构研究所 Preparation method of grapheme-lithium manganese silicate anode material
CN104009224A (en) * 2014-05-13 2014-08-27 昆明理工大学 Method for synthesizing lithium iron silicate positive electrode material by using chrysotile asbestos as raw material
CN106450186A (en) * 2016-10-10 2017-02-22 南京矽力源科技发展有限公司 Preparation method for lithium manganese silicate/carbon composite material used as positive electrode material of lithium ion battery, and positive electrode slurry and application
CN106992284A (en) * 2017-03-07 2017-07-28 武汉理工大学 Redox graphene ferrous metasilicate ferroso-ferric oxide sandwich structure compound and its preparation method and application
CN110993923A (en) * 2019-12-26 2020-04-10 惠州亿纬锂能股份有限公司 Carbon-coated auxiliary sodium-titanium double-doped lithium iron silicate positive electrode material and preparation method and application thereof
CN114883553A (en) * 2022-05-11 2022-08-09 兰州理工大学 Preparation of porous nano Li by alkali liquor selective corrosion 2 FeSiO 4 Method for preparing/C

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CN101546828A (en) * 2008-12-27 2009-09-30 深圳市德方纳米科技有限公司 Nanometer ferrous silicate lithium material and preparation method thereof
CN101807690A (en) * 2010-04-09 2010-08-18 奇瑞汽车股份有限公司 Preparation method of lithium ion battery ferric metasilicate lithium positive electrode material
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102916184A (en) * 2012-10-23 2013-02-06 中国科学院过程工程研究所 Lithium silicate compound of anode material of lithium ion battery, and preparation method and application for lithium silicate compound
CN103050692A (en) * 2012-12-21 2013-04-17 中国科学院福建物质结构研究所 Preparation method of grapheme-lithium manganese silicate anode material
CN104009224A (en) * 2014-05-13 2014-08-27 昆明理工大学 Method for synthesizing lithium iron silicate positive electrode material by using chrysotile asbestos as raw material
CN106450186A (en) * 2016-10-10 2017-02-22 南京矽力源科技发展有限公司 Preparation method for lithium manganese silicate/carbon composite material used as positive electrode material of lithium ion battery, and positive electrode slurry and application
CN106450186B (en) * 2016-10-10 2018-09-07 江苏载驰科技股份有限公司 A kind of preparation method, anode sizing agent and the application of lithium-ion battery anode material lithium manganese silicate/carbon composite
CN106992284A (en) * 2017-03-07 2017-07-28 武汉理工大学 Redox graphene ferrous metasilicate ferroso-ferric oxide sandwich structure compound and its preparation method and application
CN106992284B (en) * 2017-03-07 2019-10-01 武汉理工大学 Redox graphene-ferrous metasilicate-ferroso-ferric oxide sandwich structure compound and its preparation method and application
CN110993923A (en) * 2019-12-26 2020-04-10 惠州亿纬锂能股份有限公司 Carbon-coated auxiliary sodium-titanium double-doped lithium iron silicate positive electrode material and preparation method and application thereof
CN110993923B (en) * 2019-12-26 2021-11-23 湖北亿纬动力有限公司 Carbon-coated auxiliary sodium-titanium double-doped lithium iron silicate positive electrode material and preparation method and application thereof
CN114883553A (en) * 2022-05-11 2022-08-09 兰州理工大学 Preparation of porous nano Li by alkali liquor selective corrosion 2 FeSiO 4 Method for preparing/C

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Application publication date: 20121003