CN105355884A - High-specific-capacity lithium ion battery electrode material and preparation method thereof - Google Patents
High-specific-capacity lithium ion battery electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a high-specific-capacity lithium ion battery electrode material. The preparation method comprises the steps of oxidizing through a Hummers method, precursor solution preparing by adding pyrrole, three-dimensional gel preparing, high-temperature carbonizing and secondary hydrothermal reacting, wherein three-dimensional gel is prepared by oxidized graphene, one-dimensional carbon materials and the pyrrole through a hydrothermal self-assembly reaction, the three-dimensional gel is processed through carbonization treatment and then subjected to a co-hydrothermal reaction with transition metal salt to dope a generated transition metal oxide in a three-dimensional structure, and finally the three-dimensional self-assembled lithium ion electrode material doped with the transition metal oxide is prepared. By combining the transition metal oxide particles with the three-dimensional carbon structure, the active substances in the electrode material are evenly dispersed, and the excellent conductive property and circulating ratio capacity are achieved; meanwhile, the preparation method is simple and low in preparation cost. The invention further provides the high-specific-capacity lithium ion battery electrode material.
Description
Technical field
The invention belongs to chemical material field, especially relate to a kind of lithium ion battery electrode material and preparation method thereof.
Background technology
Current energy source, environmental problem generally become the most thorny two large problems in countries in the world, develop and utilize secondary energy sources to be the breach of dealing with problems.The material that lithium ion battery has that high-energy-density, operating voltage are high, memory-less effect etc. is regarded as having most in secondary energy sources development potentiality, it is all widely used at portable type electronic product, household electrical appliance, the vehicles etc.But existing commercialization negative material mainly graphite, its theoretical specific capacity only has 372mAh/g, is difficult to meet lithium ion battery at powerful device as the application such as electric motor car, electrical network.Therefore, needing to find and exploitation is efficient, low consumption and cheap negative material replace graphite to be the key of dealing with problems, is also study hotspot and difficult point.Transition metal oxide has the theoretical specific capacity of higher than graphite 2 ~ 3 times usually, lower discharge platform, but to there is in charge and discharge process large and this two large Important Problems of poorly conductive of volumetric expansion, thus causes that its capacity attenuation is rapid, cyclical stability is poor.
Recent study persons have carried out a series of research work to above problem, the transition oxide by designing and prepare nanometer had, or its chemical property made moderate progress by having the strategies such as the conductive carbon based of mesoporous/micropore and transition metal compound but also has the following disadvantages: 1) nanometer particle very easily reunite, skewness; 2) general porous, electrically conductive substrate is electrochemically inactive material, and the overall volume specific capacity of material is low.Graphene is as electrochemical active material, the reversible storage of lithium ion at it can be realized, there is star's material that bigger serface, good compliance and conductivity become transition metal compounding simultaneously, but there is serious stacking phenomenon between layers in Graphene.
In order to overcome Graphene directly and the graphene dispersion brought of transition metal compound is uneven, serious phenomenon reunited by transition metal, researcher makes the transition metal grown be dispersed in the method for the preparation on graphene sheet layer under adopting high-temperature and high-pressure conditions, or utilizes the methods such as the structure of the well-designed Graphenes such as template to solve.These method relative complex, high costs, be unfavorable for industrialized preparation and production.
Summary of the invention
The present invention is for solving the problem and proposing, provide a kind of height ratio capacity lithium ion battery electrode material and preparation method thereof, electrode material prepared by the method has three-dimensional stability structure, active material can be made to be uniformly dispersed and the feature that system conducts electricity very well, recycle ratio capacity is high, be the height ratio capacity lithium ion battery electrode material of the three-dimensional self assembly based on Graphene compound.
Height ratio capacity lithium ion battery electrode material provided by the invention, it is complex carbon material, it is characterized in that: be 30 ~ 80% containing transition metal oxide mass fraction.
Height ratio capacity lithium ion battery electrode material provided by the invention, can also have such feature: wherein, and transition metal oxide is any one in tin, cobalt, manganese, iron, copper, nickel, tungsten, molybdenum, titanium oxide
The present invention also provides a kind of height ratio capacity lithium ion battery electrode material preparation method, comprises the following steps:
Step one, the graphene oxide, one dimension material with carbon element inorganic acid and the deionized water that are adopted by graphite Hummers method oxidation processes to obtain wash down, and are made into graphene oxide water solution and the one dimension material with carbon element aqueous solution of suitable concn respectively;
Step 2, by after in step one, graphene oxide water solution, the one dimension material with carbon element aqueous solution carry out ultrasonic disperse respectively by certain mass than mixing and adding the pyrroles of certain mass mark, obtained precursor solution;
Step 3, utilize hydro-thermal reaction to carry out first time hydro-thermal reaction to the precursor solution obtained by step 2, then freeze drying, obtains three dimensional gel;
Step 4, the three dimensional gel that step 3 is obtained carries out high temperature cabonization;
Step 5, second time hydro-thermal reaction is carried out after being mixed with transition metal salt by product after high temperature cabonization in step 4, solid product filtration obtained, through repeatedly deionized water, alcoholic solvent cleaning, obtains the li-ion electrode materials of the three-dimensional self assembly of containing transition metal oxide.
Height ratio capacity lithium ion battery electrode material preparation method provided by the invention, can also have such feature: wherein, and wherein, inorganic acid is any one or its mixed acid in hydrochloric acid, sulfuric acid, nitric acid.
Height ratio capacity lithium ion battery electrode material preparation method provided by the invention, can also have such feature: wherein, and wherein, in step one, suitable concn is 7 ~ 15mg/ml.
Height ratio capacity lithium ion battery electrode material preparation method provided by the invention, such feature can also be had: wherein, in step 2, certain mass ratio is graphene oxide water solution quality: one dimension material with carbon element aqueous solution quality is 1:3 ~ 3:1, and certain mass mark is 1 ~ 5%.
Height ratio capacity lithium ion battery electrode material preparation method provided by the invention, such feature can also be had: wherein, in step 3, hydrothermal reaction condition is at 160 ~ 200 DEG C of temperature 10 ~ 16 hours first time, and cryodesiccated condition be maintenance 24 ~ 72 hours at-40 DEG C ~-80 DEG C temperature.
Height ratio capacity lithium ion battery electrode material preparation method provided by the invention, can also have such feature: wherein, and the condition of step 4 high temperature cabonization keeps 1 ~ 4 hour at 800 ~ 1200 DEG C of temperature.
Height ratio capacity lithium ion battery electrode material preparation method provided by the invention, such feature can also be had: wherein, in step one, one dimension material with carbon element refers to any one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, carbon nano rod, carbon nanocoils, carbon nanometer rod, carbon fiber, and in step 5, transition metal salt is any one in tin, cobalt, manganese, iron, copper, nickel, tungsten, molybdenum, the nitrate of titanium and hydrochloride.
Height ratio capacity lithium ion battery electrode material preparation method provided by the invention, can also have such feature: wherein, and in step 5, the condition of second time hydro-thermal reaction is at 180 ~ 220 DEG C of temperature 12 ~ 20 hours.
Invention effect and effect
Height ratio capacity lithium ion battery electrode material provided by the invention and preparation method thereof, utilize graphene oxide, one dimension material with carbon element and pyrroles prepare three dimensional gel by hydro-thermal self-assembling reaction, hydro-thermal reaction is total to thus the li-ion electrode materials of the three-dimensional self assembly of finally preparing containing transition metal oxide in a three-dimensional structure of being adulterated by the transition metal oxide of generation with transition metal salt again after carbonization treatment, by transition metal oxide particle and three-dimensional carbon structure combined, make the active material in electrode material reach dispersed and there is excellent electric conductivity and recycle ratio capacity, this preparation method is simple simultaneously, preparation cost is low.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of height ratio capacity lithium ion battery electrode material preparation method of the present invention;
Fig. 2 is after height ratio capacity lithium ion battery electrode material of the present invention is made into the negative pole of lithium battery, the capacity of this battery and the curve chart of efficiency for charge-discharge;
Fig. 3 is after height ratio capacity lithium ion battery electrode material of the present invention is made into the negative pole of lithium battery, the discharge capacity curve chart under 0.5mA/g ~ 10A/g charging and discharging currents density of this battery.
Embodiment
The technological means realized to make the present invention, creation characteristic, reach object and effect is easy to understand, following examples are specifically addressed height ratio capacity lithium ion battery electrode material preparation method of the present invention by reference to the accompanying drawings.
Embodiment 1
Fig. 1 is the schematic flow sheet of the height ratio capacity lithium ion battery electrode material preparation method of the present embodiment
Step one S1, oxidation.Graphite is adopted Hummers method (W.S.Hummers, R.E.Hoffeman, J.Am.Chem.Soc.1958,80,1339) oxidation processes obtains graphene oxide, one dimension material with carbon element hydrochloric acid and deionized water wash down, and are made into the aqueous solution of 10mg/ml respectively;
Step 2 S2, prepares precursor solution.By step one gained graphene oxide, one dimension material with carbon element, after carrying out ultrasonic disperse 30min respectively, 1:1 mixes and adds mass fraction is in mass ratio 2% pyrroles, thus obtained precursor solution;
Step 3 S3, prepares three dimensional gel.Utilize hydro-thermal reaction to carry out the hydro-thermal reaction of 12h at 180 DEG C to the precursor solution obtained by step 2, then at-50 DEG C of freeze drying 48h, obtain three dimensional gel;
Step 4 S4, high temperature cabonization.After the three dimensional gel that step 3 is obtained is placed in 1050 DEG C of high temperature cabonization 2h,
Step 5 S5, second time hydro-thermal reaction.By the product after high temperature cabonization in step 4 and transition metal salt, the present embodiment carries out the hydro-thermal reaction of 16h at second time 200 DEG C after using copper nitrate mixing, again through repeatedly deionized water, ethanol purge, thus the li-ion electrode materials of the three-dimensional self assembly of obtained containing transition metal oxide.
Embodiment 2
Step one S1, oxidation.Graphite is adopted Hummers method (W.S.Hummers, R.E.Hoffeman, J.Am.Chem.Soc.1958,80,1339) oxidation processes obtains graphene oxide, one dimension material with carbon element hydrochloric acid and deionized water wash down, and are made into the aqueous solution of 7mg/ml respectively;
Step 2 S2, prepares precursor solution.By step one gained graphene oxide, one dimension material with carbon element, after carrying out ultrasonic disperse 30min respectively, 1:3 mixes and adds mass fraction is in mass ratio 1% pyrroles, thus obtained precursor solution;
Step 3 S3, prepares three dimensional gel.Utilize hydro-thermal reaction to carry out the hydro-thermal reaction of 16h at 160 DEG C to the precursor solution obtained by step 2, then at-40 DEG C of freeze drying 72h, obtain three dimensional gel;
Step 4 S4, high temperature cabonization.After the three dimensional gel that step 3 is obtained is placed in 800 DEG C of high temperature cabonization 4h,
Step 5 S5, second time hydro-thermal reaction.By the product after high temperature cabonization in step 4 and transition metal salt, the present embodiment carries out the hydro-thermal reaction of 20h at second time 180 DEG C after using ferric nitrate mixing, again through repeatedly deionized water, ethanol purge, thus the li-ion electrode materials of the three-dimensional self assembly of obtained containing transition metal oxide.
Embodiment 3
Step one S1, oxidation.Graphite is adopted Hummers method (W.S.Hummers, R.E.Hoffeman, J.Am.Chem.Soc.1958,80,1339) oxidation processes obtains graphene oxide, one dimension material with carbon element hydrochloric acid and deionized water wash down, and are made into the aqueous solution of 15mg/ml respectively;
Step 2 S2, prepares precursor solution.By step one gained graphene oxide, one dimension material with carbon element, after carrying out ultrasonic disperse 60min respectively, 3:1 mixes and adds mass fraction is in mass ratio 5% pyrroles, thus obtained precursor solution;
Step 3 S3, prepares three dimensional gel.Utilize hydro-thermal reaction to carry out the hydro-thermal reaction of 10h at 200 DEG C to the precursor solution obtained by step 2, then at-80 DEG C of freeze drying 24h, obtain three dimensional gel;
Step 4 S4, high temperature cabonization.After the three dimensional gel that step 3 is obtained is placed in 1200 DEG C of high temperature cabonization 1h,
Step 5 S5, second time hydro-thermal reaction.By the product after high temperature cabonization in step 4 and transition metal salt, the present embodiment carries out the hydro-thermal reaction of 12h at second time 220 DEG C after using titanium tetrachloride mixing, again through repeatedly deionized water, ethanol purge, thus the li-ion electrode materials of the three-dimensional self assembly of obtained containing transition metal oxide.
Through test, record embodiment 1 respectively, 2, the transition metal oxide mass fraction (with oxide the most stable under normal condition conversion) in 3
Test by analysis, electrode material prepared by said method is carbon composite, comprises above-mentioned transition metal oxide and complex carbon material.
In order to the high power capacity of li-ion electrode materials in the present embodiment is described through a step, carry out the electricity test of material below.
Fig. 2 is after the height ratio capacity lithium ion battery electrode material in this enforcement is made into the negative pole of lithium battery, the capacity of this battery and the curve chart of efficiency for charge-discharge
The electrode material of the embodiment of the present invention 1 is made into the negative pole of lithium battery, and using this lithium battery as tested object, the multi-channel battery test instrument that the model utilizing Wuhan Land Electronic Co., Ltd. to manufacture is CT2001A carries out electrochemical property test to this tested object, the charging/discharging voltage window of test is 0.001 ~ 3V, charging and discharging currents is 100mA/g, measured capacity and the curve chart of efficiency for charge-discharge are as shown in Figure 1, the transverse axis of Fig. 1 is cycle-index number axis, righthand vertical axis in Fig. 1 is coulombic efficiency number axis, lefthand vertical axis in Fig. 1 is capacity number axis, curve 1 in Fig. 1 is coulombic efficiency curve, curve 2 in Fig. 1 is capacity curve, as can be seen from Figure 1, the discharge capacity first of tested object is at about 1700mAh/g, after 100 charge and discharge cycles, the capacity stablizes of tested object is at 600mAh/g, and except front circulation several times, coulombic efficiency maintains more than 95% all the time, tested object has high power capacity and excellent cycling stability as can be seen here.
Fig. 3 is after the height ratio capacity lithium ion battery electrode material of the present embodiment is made into the negative pole of lithium battery, the discharge capacity curve chart under 0.5mA/g ~ 10A/g charging and discharging currents density of this battery
The electrode material of the embodiment of the present invention 1 is made into the negative pole of lithium battery, and using this lithium battery as tested object, the multi-channel battery test instrument that the model utilizing Wuhan Land Electronic Co., Ltd. to manufacture is CT2001A carries out electrochemical property test to this tested object, the measured discharge capacity curve under 0.5mA/g ~ 10A/g charging and discharging currents density as shown in Figure 2, as can be seen from Figure 2, this tested object is under different current density condition, still there is higher capacity, especially under the current density that 10A/g is so high, battery still has certain capacity, and under 0.1A/g current density, the capacity of about 600mAh/g can be returned to again completely thereupon.
The effect of embodiment and beneficial effect
This series implements height ratio capacity lithium ion battery electrode material provided and preparation method thereof, utilize graphene oxide, one dimension material with carbon element and pyrroles prepare three dimensional gel by hydro-thermal self-assembling reaction, hydro-thermal reaction is total to thus the li-ion electrode materials of the three-dimensional self assembly of finally preparing containing transition metal oxide in a three-dimensional structure of being adulterated by the transition metal oxide of generation with transition metal salt again after carbonization treatment, by transition metal oxide particle and three-dimensional carbon structure combined, make the active material in electrode material reach dispersed and there is excellent electric conductivity and recycle ratio capacity, this preparation method is simple simultaneously, preparation cost is low.
Claims (10)
1. a height ratio capacity lithium ion battery electrode material, it is complex carbon material, it is characterized in that:
Be 30 ~ 80% containing transition metal oxide mass fraction.
2. height ratio capacity lithium ion battery electrode material according to claim 1, is characterized in that:
Wherein, described transition metal oxide is any one in tin, cobalt, manganese, iron, copper, nickel, tungsten, molybdenum, titanium oxide.
3. a height ratio capacity lithium ion battery electrode material preparation method, is characterized in that, comprises the following steps:
Step one, the graphene oxide, one dimension material with carbon element inorganic acid and the deionized water that are adopted by graphite Hummers method oxidation processes to obtain wash down, and are made into graphene oxide water solution and the one dimension material with carbon element aqueous solution of suitable concn respectively;
Step 2, after graphene oxide water solution described in step one, the described one dimension material with carbon element aqueous solution are carried out ultrasonic disperse respectively by certain mass than mixing and adding the pyrroles of certain mass mark, obtained precursor solution;
Step 3, utilize hydro-thermal reaction to carry out first time hydro-thermal reaction to the described precursor solution obtained by step 2, then freeze drying, obtains three dimensional gel;
Step 4, the described three dimensional gel that step 3 is obtained carries out high temperature cabonization;
Step 5, second time hydro-thermal reaction is carried out after being mixed with transition metal salt by product after high temperature cabonization in step 4, solid product filtration obtained, through repeatedly deionized water, alcoholic solvent cleaning, obtains the li-ion electrode materials of the three-dimensional self assembly of containing transition metal oxide.
4. height ratio capacity lithium ion battery electrode material preparation method according to claim 3, is characterized in that:
Wherein, inorganic acid is any one or its mixed acid in hydrochloric acid, sulfuric acid, nitric acid.
5. height ratio capacity lithium ion battery electrode material preparation method according to claim 3, is characterized in that:
Wherein, suitable concn described in step one is 7 ~ 15mg/ml.
6. height ratio capacity lithium ion battery electrode material preparation method according to claim 3, is characterized in that:
Wherein, the ratio of certain mass described in step 2 is described graphene oxide water solution quality: described one dimension material with carbon element aqueous solution quality is 1:3 ~ 3:1, and described certain mass mark is 1 ~ 5%.
7. height ratio capacity lithium ion battery electrode material preparation method according to claim 3, is characterized in that:
Wherein, first time described in step 3 hydrothermal reaction condition be at 160 ~ 200 DEG C of temperature 10 ~ 16 hours, described cryodesiccated condition be maintenance 24 ~ 72 hours at-40 DEG C ~-80 DEG C temperature.
8. height ratio capacity lithium ion battery electrode material preparation method according to claim 3, is characterized in that:
Wherein, the condition of high temperature cabonization described in step 4 keeps 1 ~ 4 hour at 800 ~ 1200 DEG C of temperature.
9. height ratio capacity lithium ion battery electrode material preparation method according to claim 3, is characterized in that:
Wherein, the material with carbon element of one dimension described in step one refer in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, carbon nano rod, carbon nanocoils, carbon nanometer rod, carbon fiber any one,
Transition metal salt described in step 5 is any one in tin, cobalt, manganese, iron, copper, nickel, tungsten, molybdenum, the nitrate of titanium and hydrochloride.
10. height ratio capacity lithium ion battery electrode material preparation method according to claim 3, is characterized in that:
Wherein, the condition of the hydro-thermal reaction of second time described in step 5 is at 180 ~ 220 DEG C of temperature 12 ~ 20 hours.
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| CN105810917A (en) * | 2016-05-24 | 2016-07-27 | 刘高志 | Preparation of SnO2-Cr2O3-graphene composite and application thereof in negative electrode of lithium ion cell |
| CN106848229A (en) * | 2017-02-03 | 2017-06-13 | 南京邮电大学 | A kind of metallo-organic compound cathode material preparation method |
| CN107316999A (en) * | 2017-06-06 | 2017-11-03 | 上海理工大学 | A kind of li-ion electrode materials of three-dimensional self assembly being combined based on graphene and preparation method thereof |
| CN107808779A (en) * | 2016-09-08 | 2018-03-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | CNT/three-dimensional graphene composite material, its preparation method and application |
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| CN108550824A (en) * | 2018-04-28 | 2018-09-18 | 上海理工大学 | A kind of high-capacity battery cathode material preparation method |
| CN110635127A (en) * | 2019-10-31 | 2019-12-31 | 扬州工业职业技术学院 | Lithium ion battery electrode material based on metal molybdate compound nano material |
| CN111628176A (en) * | 2020-06-17 | 2020-09-04 | 苏州盟维动力科技有限公司 | Multi-component three-dimensional conductive carbon network, self-supporting composite electrode, and preparation methods and applications thereof |
| CN113130862A (en) * | 2021-03-10 | 2021-07-16 | 东南大学 | Three-dimensional graphene composite material and preparation method and application thereof |
| CN114068195A (en) * | 2021-11-18 | 2022-02-18 | 四川金汇能新材料股份有限公司 | Metal-compounded carbon negative electrode material and preparation method thereof |
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