CN105390682A - Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material - Google Patents
Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a preparation method for a lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and an application of the composite electrode material. According to the method, a ''spherical iron source'' is taken as a template of a three-dimensional structure, and the lithium iron phosphate microsphere/three-dimensional graphene composite electrode material is constructed in one step with a high-temperature reduction method; and due to a unique spherical structure of lithium iron phosphate and a favorable three-dimensional structure of graphene, the composite electrode material solves the problems of relatively low tap density, lithium ion diffusion blocking, rate performance defect and the like of a current graphene-coated LiFePO4 nano composite material; and comprehensive goals of high electronic conductivity, high ionic conductance, high tap density and high power density and energy density are achieved, and a new technology is provided for development of high-performance LiFePO4 lithium ion battery positive electrode materials.
Description
Technical field
The present invention relates to lithium ion battery electrode material preparing technical field, more specifically, relate to preparation method and the application thereof of a kind of LiFePO4 microballoon/three-dimensional grapheme combination electrode material.
Background technology
LiFePO4 (LiFePO
4) be the positive electrode of most prospect in current power type lithium ion battery applications, this material has the plurality of advantages such as abundant raw material, moderate cost, environmental friendliness, fail safe are high, stable cycle performance; But, LiFePO
4electronic conductivity and lithium ion diffusion rate all lower, causing its capacity when high current charge-discharge lower, is namely that high rate capability is poor, constrains the application of this material in electrokinetic cell field and popularization to a great extent.
Take high conductive material (such as amorphous carbon and conducting polymer) coated and design nano particle, effectively can improve LiFePO
4electronic conductivity, thus certain degree improves high rate performance.But the tight clad structure of electric conducting material greatly reduces LiFePO
4the lithium ion conduction ability of material, and nano particle scheme result in LiFePO more
4the actual tap density of material significantly reduces.As everyone knows, the ionic conduction ability of lithium ion battery electrode material and tap density, be closely related with the power density of battery and energy density in actual applications.Therefore, at exploitation " electric conducting material " cladded type LiFePO
4in materials process, while effectively improving " electronic conductivity " of material, guarantee that higher " ionic conductance " and desirable " tap density " are very important.
Usually, if LiFePO
4the particle of material is less, and coated material is more, and its tap density will be lower.Particularly erose LiFePO
4encapsulated nanoparticles, its tap density is general not higher than 1.0gcm
-3.Therefore, a kind of LiFePO with regular shape is developed
4material, raising tap density and energy density is one and well selects.In numerous regular shape, spherical is the structure of a kind of regular appearance, good fluidity.Significantly, relative traditional structure, spherical LiFePO
4material has following several large potential advantages: (1) spherical structure can realize tightly packed, and namely " tap density " can improve greatly, therefore can prepare high-energy-density electrode; (2) spherome surface is smooth, specific area is low, decreases the generation with electrolyte side reaction, improves first charge-discharge efficiency; (3) in security performance, sphere material is comparatively greatly improved, and especially under the high temperature conditions, the thickness of electrode does not increase.In sum, exploitation is a kind of by miniature spherical LiFePO
4with the cladded type LiFePO that electric conducting material is formed
4microballoon combination electrode material is one of development tactics that application prospect is bright and clear.
In addition, if LiFePO
4the coating layer of material is thicker, and lithium ion is diffused into LiFePO
4the speed of material internal is slower, and coating layer is tightr, and the conducting power of lithium ion is lower.Therefore, select the clad material that a kind of conductance is high and structure is ultra-thin, to raising LiFePO
4the ionic conduction ability of material and electrode power density are vital.At present, " Graphene " nanometer sheet of latest development is expected to become high-performance LiFePO of new generation
4clad material, gives the credit to its ultra-thin two-dimension structure, superelevation conductivity and excellent physical chemical stability, graphene coated LiFePO
4material gets the attention.But most of graphene coated structures of current report are all very fine and close, and the graphene nanometer sheet that particularly a slice is larger often completely closely wraps a LiFePO
4nano particle, causes lithium ion diffusion hindered, is unfavorable for the raising of high rate performance.Therefore, develop a kind of three-dimensional grapheme material with macroporous network structure, construct LiFePO that is not exclusively coated, fractional open
4/ three-dimensional grapheme composite construction, will advantageously in raising electrode material high rate capability.
Summary of the invention
Technical problem to be solved by this invention overcomes the above-mentioned defect existed in prior art, provides the preparation method of a kind of LiFePO4 microballoon/three-dimensional grapheme combination electrode material.
Second object of the present invention is LiFePO4 microballoon/three-dimensional grapheme combination electrode material that said method prepares.
3rd object of the present invention is to provide the application of above-mentioned LiFePO4 microballoon/three-dimensional grapheme combination electrode material.
The object of the invention is to be achieved by the following technical programs:
A preparation method for LiFePO4 microballoon/three-dimensional grapheme combination electrode material, comprises the following steps:
S1. the preparation of spherical source of iron: be carry out hydro-thermal reaction under 1:0.1 ~ 0.5 is blended in 100 ~ 150 DEG C of temperature in mass ratio by ferric phosphate and carbohydrate polyol, washing is dry obtains spherical source of iron;
S2., after the spherical source of iron prepared by S1, lithium source and graphene oxide mix by a certain percentage, carry out high-temperature hot under an inert atmosphere and react and obtain LiFePO4 microballoon/three-dimensional grapheme combination electrode material; The mass ratio of described spherical source of iron and graphene oxide is 1:0.1 ~ 0.5.
First the present invention selects first to prepare spherical source of iron, spherical source of iron is utilized to mix with Graphene, final material is obtained by high-temperature hot reaction, spherical source of iron can control the shape of LiFePO4 on the one hand, and on the other hand, graphene growth is in surface, mainly through controlling the mass ratio of spherical source of iron and graphene oxide, the coverage rate that controlled oxidization Graphene shows in spherical source of iron, thus forming section is exposed, the three-dimensional structure of portion envelops.
In addition, in the method for the invention, the preparation of spherical source of iron is crucial, wherein, the temperature of hydro-thermal reaction needs to carry out strictly control, only has hydrothermal temperature to control could form the spherical of satisfactory rule at 100 ~ 150 DEG C of temperature, could be used for the compound of next step and Graphene.
Preferably, carbohydrate polyol described in S1 be selected from glucose, sucrose, starch, cellulosic one or more.
Preferably, process described in S1 is: by ferric phosphate and carbohydrate polyol in mass ratio for 1:0.1 ~ 0.5 mixes, and be scattered in appropriate deionized water, be placed in hydrothermal reaction kettle and carry out hydro-thermal reaction at 100 ~ 150 DEG C of temperature, finally washing dry obtained " spherical source of iron ", i.e. polyhydroxy ferric phosphate microballoon.
Preferably, process described in S2 is: the spherical source of iron prepared by S1, lithium source and graphene oxide are scattered in deionized water by a certain percentage, dry acquisition mixture, mixture is placed in high temperature process furnances, carry out high-temperature hot reaction under an inert atmosphere, i.e. obtained LiFePO4 microballoon/three-dimensional grapheme combination electrode material.
Preferably, lithium source described in S2 be selected from lithium acetate, lithium nitrate, lithium carbonate one or more.
Preferably, described in S2, the temperature of high-temperature hot reaction is 600 ~ 800 DEG C, and the reaction time is 5 ~ 10h, and programming rate is 1 ~ 5 DEG C/min; Inert atmosphere described in S2 be selected from nitrogen, argon gas and helium one or more.
LiFePO4 microballoon/three-dimensional grapheme combination electrode material that the present invention also provides said method to obtain.
The present invention also provides described LiFePO4 microballoon/three-dimensional grapheme combination electrode material preparing the application in lithium ion battery.
Compared with prior art, the present invention has following beneficial effect:
The invention provides the preparation method of a kind of LiFePO4 microballoon/three-dimensional grapheme combination electrode material, comprise: the preparation of the spherical source of iron of S1.: be carry out hydro-thermal reaction under 1:0.1 ~ 0.5 is blended in 100 ~ 150 DEG C of temperature in mass ratio by ferric phosphate and carbohydrate polyol, washing is dry obtains spherical source of iron; S2. after the spherical source of iron prepared by S1, lithium source and graphene oxide mix by a certain percentage, carry out high-temperature hot under an inert atmosphere react and obtain LiFePO4 microballoon/three-dimensional grapheme combination electrode material, namely using " spherical source of iron " as the template of three-dimensional structure, LiFePO4 microballoon/three-dimensional grapheme combination electrode material is built by method one step of high temperature reduction, due to the spherical structure of LiFePO4 uniqueness and the favourable three-dimensional structure of Graphene, this combination electrode material solves current graphene coated LiFePO
4the tap density of nano composite material is lower, lithium ion diffusion hindered, the problems such as high rate performance shortcoming; Achieving the integration objective of high electronic conductivity, high ion conductivity, high-tap density, high power density and energy density, is high-performance LiFePO
4the development of anode material for lithium-ion batteries provides new technology.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of " spherical source of iron " di iron prepared by embodiment 1.
Fig. 2 is the scanning electron microscope image of " spherical source of iron " di iron prepared by embodiment 1; Fig. 2 A is 30 μm of lower scanning electron microscope images; Fig. 2 B is 5 μm of lower scanning electron microscope images.
Fig. 3 is " LiFePO prepared by embodiment 1
4microballoon/three-dimensional grapheme " X-ray diffracting spectrum.
Fig. 4 is " LiFePO prepared by embodiment 1
4microballoon/three-dimensional grapheme " scanning electron microscope image; Fig. 4 A is 5 μm of lower scanning electron microscope images; Fig. 4 B is 2 μm of lower scanning electron microscope images.
Fig. 5 is " LiFePO prepared by embodiment 1
4microballoon/three-dimensional grapheme " charging and discharging curve.
Fig. 6 is the scanning electron microscope image of " source of iron " prepared by comparative example 1.
Fig. 7 is " LiFePO prepared by comparative example 2
4microballoon/three-dimensional grapheme " scanning electron microscope image.
Fig. 8 is " LiFePO prepared by comparative example 3
4microballoon/three-dimensional grapheme " scanning electron microscope image.
Embodiment
Further illustrate content of the present invention below in conjunction with Figure of description and specific embodiment, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the simple modification do the inventive method, step or condition or replacement, all belong to scope of the present invention; If do not specialize, the conventional means that technological means used in embodiment is well known to those skilled in the art.
embodiment 1
S1. the preparation of " spherical source of iron ": take 10g ferric phosphate and 1g glucose is scattered in 80ml deionized water, is placed in 100ml hydrothermal reaction kettle 120 DEG C reaction 5h, dry obtained " spherical source of iron " the polyhydroxy ferric phosphate microballoon of washing.
S2. 2g polyhydroxy ferric phosphate microballoon (by ferrous metal quality), 0.3g lithium acetate (by lithium metal quality) and 0.6g graphene oxide are scattered in deionized water, dry; Placed by said mixture in high temperature process furnances, carry out high-temperature hot reaction in a nitrogen atmosphere, reaction temperature is 750 DEG C, and the reaction time is 8h, and programming rate is 2 DEG C/min; I.e. obtained " LiFePO
4microballoon/three-dimensional grapheme " composite material.
" spherical source of iron " crystallinity prepared by said method is good and be evenly distributed, and average diameter is about 4.5 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 4.0 μm, and the coverage rate of Graphene to LiFePO4 is about 80%; Based on LiFePO
4the fractional open composite construction of microballoon and three-dimensional grapheme is successfully prepared.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 160mAhg
-1and 121mAhg
-1.Fig. 1 is the X-ray diffracting spectrum of " spherical source of iron " di iron prepared by the present embodiment; Fig. 2 is the scanning electron microscope image of " spherical source of iron " di iron prepared by the present embodiment; Fig. 3 is " LiFePO prepared by the present embodiment
4microballoon/three-dimensional grapheme " X-ray diffracting spectrum; Fig. 4 is " LiFePO prepared by the present embodiment
4microballoon/three-dimensional grapheme " scanning electron microscope image; Fig. 5 is " LiFePO prepared by the present embodiment
4microballoon/three-dimensional grapheme " charging and discharging curve.
embodiment 2
S1. the preparation of " spherical source of iron ": take 10g ferric phosphate and 1g glucose is scattered in 80ml deionized water, is placed in 100ml hydrothermal reaction kettle 100 DEG C reaction 5h, dry obtained " spherical source of iron " the polyhydroxy ferric phosphate microballoon of washing.
S2. 2g polyhydroxy ferric phosphate microballoon (by ferrous metal quality), 0.3g lithium acetate (by lithium metal quality) and 0.6g graphene oxide are scattered in deionized water, dry; Placed by said mixture in high temperature process furnances, carry out high-temperature hot reaction in a nitrogen atmosphere, reaction temperature is 750 DEG C, and the reaction time is 8h, and programming rate is 2 DEG C/min; I.e. obtained " LiFePO
4microballoon/three-dimensional grapheme " composite material.
" spherical source of iron " crystallinity prepared by said method is good and be evenly distributed, and average diameter is about 3 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 2.5 μm, and the coverage rate of Graphene to LiFePO4 is about 90%; Based on LiFePO
4the fractional open composite construction of microballoon and three-dimensional grapheme is successfully prepared.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 152mAhg
-1and 114mAhg
-1.
embodiment 3
S1. the preparation of " spherical source of iron ": take 10g ferric phosphate and 1g glucose is scattered in 80ml deionized water, is placed in 100ml hydrothermal reaction kettle 150 DEG C reaction 5h, dry obtained " spherical source of iron " the polyhydroxy ferric phosphate microballoon of washing.
S2. 2g polyhydroxy ferric phosphate microballoon (by ferrous metal quality), 0.3g lithium acetate (by lithium metal quality) and 0.6g graphene oxide are scattered in deionized water, dry; Placed by said mixture in high temperature process furnances, carry out high-temperature hot reaction in a nitrogen atmosphere, reaction temperature is 750 DEG C, and the reaction time is 8h, and programming rate is 2 DEG C/min; I.e. obtained " LiFePO
4microballoon/three-dimensional grapheme " composite material.
" spherical source of iron " crystallinity prepared by said method is good and be evenly distributed, and average diameter is about 6 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 5 μm, and the coverage rate of Graphene to LiFePO4 is about 70%; Based on LiFePO
4the fractional open composite construction of microballoon and three-dimensional grapheme is successfully prepared.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 154mAhg
-1and 115mAhg
-1.
embodiment 4
Experimental technique is with embodiment 1, and the consumption uniquely unlike graphene oxide changes 0.4g into.
" spherical source of iron " crystallinity prepared by said method is good and be evenly distributed, and average diameter is about 4.5 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 4.0 μm, and the coverage rate of Graphene to LiFePO4 is about 60%; Based on LiFePO
4the fractional open composite construction of microballoon and three-dimensional grapheme is successfully prepared.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 154mAhg
-1and 118mAhg
-1.
embodiment 5
Experimental technique is with embodiment 1, and the consumption uniquely unlike graphene oxide changes 0.8g into.
" spherical source of iron " crystallinity prepared by said method is good and be evenly distributed, and average diameter is about 4.5 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 4.0 μm, and the coverage rate of Graphene to LiFePO4 is about 90%; Based on LiFePO
4the fractional open composite construction of microballoon and three-dimensional grapheme is successfully prepared.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 151mAhg
-1and 113mAhg
-1.
embodiment 6
Experimental technique with embodiment 1, uniquely unlike, replace the glucose of 1g with 3g starch.
" spherical source of iron " crystallinity prepared by the present embodiment method is good and be evenly distributed, and average diameter is about 6.0 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 5.5 μm, and the coverage rate of Graphene to LiFePO4 is about 60%; Based on LiFePO
4the fractional open composite construction of microballoon and three-dimensional grapheme is successfully prepared.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 152mAhg
-1and 111mAhg
-1.
embodiment 7
Experimental technique with embodiment 1, uniquely unlike, replace the glucose of 1g with 5g cellulose.
" spherical source of iron " crystallinity prepared by the present embodiment method is good and be evenly distributed, and average diameter is about 7.0 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 6.5 μm, and the coverage rate of Graphene to LiFePO4 is about 50%; Based on LiFePO
4the fractional open composite construction of microballoon and three-dimensional grapheme is successfully prepared.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 147mAhg
-1and 108mAhg
-1.
comparative example 1
Experimental technique, with embodiment 1, uniquely changes 180 DEG C into unlike the temperature in hydrothermal reaction kettle." source of iron " that this condition obtains is no longer good spherical structure, becomes irregular polyhedron; Therefore next step " LiFePO cannot be carried out
4microballoon/three-dimensional grapheme " preparation of composite material, under the ESEM of this comparative example gained " source of iron " as shown in Figure 6.
comparative example 2
Experimental technique is with embodiment 1, and the consumption uniquely unlike graphene oxide changes 0.2g into.
" spherical source of iron " crystallinity prepared by said method is good and be evenly distributed, and average diameter is about 4.5 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 4.0 μm, and the coverage rate of Graphene to LiFePO4 is about 40%; LiFePO
4it is the composite construction that major part opens that microballoon and three-dimensional grapheme define.Under the ESEM of this comparative example products obtained therefrom as shown in Figure 7.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 142mAhg
-1and 107mAhg
-1, because coverage rate is too low, specific discharge capacity obviously declines.
comparative example 3
Experimental technique is with embodiment 1, and the consumption uniquely unlike graphene oxide changes 1.0g into.
" spherical source of iron " crystallinity prepared by said method is good and be evenly distributed, and average diameter is about 4.5 μm; Prepared " LiFePO
4microballoon/three-dimensional grapheme " in LiFePO
4microballoon average diameter is about 4.0 μm, and Graphene is to the coverage rate height 100% of LiFePO4; LiFePO
4it is completely coated composite construction that microballoon and three-dimensional grapheme define.Under the ESEM of this comparative example products obtained therefrom as shown in Figure 8.This composite material specific discharge capacity under 0.1C and 5C multiplying power is respectively 138mAhg
-1and 95mAhg
-1, because coverage rate is too high, specific discharge capacity declines to a great extent.
Claims (7)
1. a preparation method for LiFePO4 microballoon/three-dimensional grapheme combination electrode material, is characterized in that, comprise the following steps:
S1. the preparation of spherical source of iron: be carry out hydro-thermal reaction under 1:0.1 ~ 0.5 is blended in 100 ~ 150 DEG C of temperature in mass ratio by ferric phosphate and carbohydrate polyol, washing is dry obtains spherical source of iron;
S2., after the spherical source of iron prepared by S1, lithium source and graphene oxide mix by a certain percentage, carry out high-temperature hot under an inert atmosphere and react and obtain LiFePO4 microballoon/three-dimensional grapheme combination electrode material; The mass ratio of described spherical source of iron and graphene oxide is 1:0.1 ~ 0.5.
2. preparation method according to claim 1, is characterized in that, carbohydrate polyol described in S1 be selected from glucose, sucrose, starch, cellulosic one or more.
3. preparation method according to claim 1, is characterized in that, lithium source described in S2 be selected from lithium acetate, lithium nitrate, lithium carbonate one or more.
4. preparation method according to claim 1, is characterized in that, described in S2, the temperature of high-temperature hot reaction is 600 ~ 800 DEG C, and the reaction time is 5 ~ 10h, and programming rate is 1 ~ 5 DEG C/min.
5. preparation method according to claim 1, is characterized in that, inert atmosphere described in S2 be selected from nitrogen, argon gas and helium one or more.
6. LiFePO4 microballoon/three-dimensional grapheme combination electrode material of obtaining of method described in any one of claim 1 to 5.
7. described in claim 6, LiFePO4 microballoon/three-dimensional grapheme combination electrode material is preparing the application in lithium ion battery.
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| CN106129387A (en) * | 2016-09-23 | 2016-11-16 | 河北工业大学 | A kind of preparation method of iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite |
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| CN110364682A (en) * | 2018-04-11 | 2019-10-22 | 广州墨羲科技有限公司 | A kind of three-dimensional grapheme microballoon composite material |
| CN110581275A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | Graphene/soft carbon negative electrode material of lithium ion battery, preparation method of graphene/soft carbon negative electrode material and lithium ion battery |
| CN111293294A (en) * | 2020-02-22 | 2020-06-16 | 电子科技大学 | Method for synthesizing lithium iron phosphate/graphene composite material by template method in one step |
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| CN106129388A (en) * | 2016-09-23 | 2016-11-16 | 河北工业大学 | A kind of preparation method of LiFePO4/three-dimensional carbon skeleton/carbon composite |
| CN106129387A (en) * | 2016-09-23 | 2016-11-16 | 河北工业大学 | A kind of preparation method of iron manganese phosphate for lithium/three-dimensional carbon skeleton/carbon composite |
| CN108807919A (en) * | 2016-09-23 | 2018-11-13 | 河北工业大学 | A kind of preparation method of three-dimensional carbon skeleton |
| CN108807919B (en) * | 2016-09-23 | 2021-01-19 | 河北工业大学 | Preparation method of three-dimensional carbon skeleton |
| CN107488267A (en) * | 2017-07-18 | 2017-12-19 | 电子科技大学 | High resistive redox grapheme material being modified based on bead and preparation method thereof |
| CN107488267B (en) * | 2017-07-18 | 2020-12-29 | 电子科技大学 | High-resistance-change redox graphene material based on small ball modification and preparation method thereof |
| CN110364682A (en) * | 2018-04-11 | 2019-10-22 | 广州墨羲科技有限公司 | A kind of three-dimensional grapheme microballoon composite material |
| CN110581275A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | Graphene/soft carbon negative electrode material of lithium ion battery, preparation method of graphene/soft carbon negative electrode material and lithium ion battery |
| CN111293294A (en) * | 2020-02-22 | 2020-06-16 | 电子科技大学 | Method for synthesizing lithium iron phosphate/graphene composite material by template method in one step |
| CN111293294B (en) * | 2020-02-22 | 2022-04-22 | 电子科技大学 | Method for synthesizing lithium iron phosphate/graphene composite material by template method in one step |
| CN116354325A (en) * | 2022-12-26 | 2023-06-30 | 蜂巢能源科技(无锡)有限公司 | Positive electrode material, preparation method thereof and lithium ion battery |
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