CN104638257A - Nano-scale manganese monoxide-conductive carbon black composite material and synthetic method thereof - Google Patents
Nano-scale manganese monoxide-conductive carbon black composite material and synthetic method thereof Download PDFInfo
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- CN104638257A CN104638257A CN201510032616.1A CN201510032616A CN104638257A CN 104638257 A CN104638257 A CN 104638257A CN 201510032616 A CN201510032616 A CN 201510032616A CN 104638257 A CN104638257 A CN 104638257A
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- composite material
- conductive black
- black composite
- carbon black
- manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a nano-scale manganese monoxide-conductive carbon black composite material and a synthetic method thereof. According to the synthetic method, a commercial low-cost conductive carbon black is used as a substrate to have oxidation-reduction reaction with potassium permanganate. The synthetic method comprises the following steps: generating nano-scale manganese oxide nano sheet-conductive carbon black composite particles at first, and then roasting in a reducing atmosphere or inert atmosphere to obtain a final nano-scale manganese monoxide-conductive carbon black composite material. The process is simple in operation, accords with environmental requirements, and is low in reaction equipment requirement, low in production cost and very suitable for industrial production. The prepared manganese monoxide-conductive carbon black composite material has excellent performance when being applied to a cathode of a lithium ion battery.
Description
Technical field
The present invention relates to the sub-manganese-conductive black composite material of a kind of nanoscale and synthetic method thereof, belong to technical field of lithium ion battery electrode.
Background technology
Lithium ion battery is a kind of important chemical energy storage device received much concern at present.Due to it, to have energy density large, lightweight, memory-less effect, the multiple advantages such as the life-span is long, and at present with mobile phone, notebook computer is be widely used as energy-storage units in portable, personal electronics's device of representative.Lithium ion battery progressively moves towards the application such as electric powered motor field and jumbo accumulation power supply now, the performance of new application to lithium ion battery is had higher requirement, and improves, optimizes that even to substitute be one of current study hotspot to the electrode material of conventional lithium ion battery and technology.
The commercialization negative material of conventional lithium ion battery is graphite, and it is with low cost, production technology relative maturity, therefore becomes the negative material of most extensive use.But, lower (the theoretical capacity 372mAh g of graphite cathode specific capacity
-1), perform poor under the condition of high current charge-discharge, and the electrode fail safe under big current also exists hidden danger, these problems make conventional graphite negative material on the new opplication in the fields such as automobile power cell, have very large difficulty.
Along with the development of nanometer technology, it is found that many transition oxide have very high electro-chemical activity after nanometer, the negative material as high performance lithium ion battery has very large using value.Wherein, manganese-base oxide aboundresources, and with other metal oxide negative material (SnO
2, Co
3o
4) compare, the multiple advantages such as have cheap, environment is affine, and electrochemical cycle stability is good, thus become the quite potential dynamic lithium battery negative material of a class.In manganese based material, manganous oxide material has higher bulk density, lower lagging voltage (< 0.8V vs Li/Li
+) and higher capacity, there is outstanding application prospect.But its lower intrinsic conductivity limits the electrochemistry performance under its big current, becomes one of business-like bottleneck of manganous oxide electrode.
Nanometer can reduce the particle size of material, effectively shortens electronics and the transmission path of lithium ion in manganous oxide negative material, in addition, carries out being complex as with carbon a kind of effective way promoting manganous oxide electrode material conductivity.Designing and preparing the manganous oxide/carbon composite with nanostructure and high electrochemical activity applies significant to its large-scale commercial.
Summary of the invention
The object of the invention is to provide nanoscale sub-manganese-conductive black composite material to improve the deficiencies in the prior art, another object of the present invention is to provide the synthetic method of above-mentioned material, and the present invention also has an object to be to provide the application of above-mentioned material in lithium ion battery negative.
Technical scheme of the present invention is: the sub-manganese-conductive black composite material of nanoscale, is characterized in that the mass ratio of manganous oxide and conductive carbon black in composite material is 0.5-2.5:1; Its primary particle size is 50nm-80nm.
Present invention also offers the method for the above-mentioned manganous oxide-conductive black composite material of synthesis, its concrete steps are:
1) potassium permanganate and deionized water are made into liquor potassic permanganate, and are uniformly mixed homogeneous with conductive black, wherein the mass ratio of conductive black and potassium permanganate is 1:(1-4);
2) by above-mentioned steps 1) mixture that obtains reacts 6-16h at 60-80 DEG C, by product washing with dry, obtain manganese oxide-conductive black compound;
3) by above-mentioned steps 2) manganese oxide-conductive black compound of obtaining under reduction atmosphere or inert atmosphere, at 400-700 DEG C of roasting 2-5h, obtain the sub-manganese-conductive black composite material of nanoscale.
Preferred steps 1) described in the mass concentration of liquor potassic permanganate be 0.2-0.8%.Preferred steps 3) described in protective atmosphere or reducing atmosphere be by passing at least one gases such as nitrogen, argon gas, carbon dioxide, helium, ammonia, hydrogen, hydrogen-argon-mixed or hydrogen nitrogen mixed gas in reaction system.
Preferred steps 3) in heating rate 1-5 DEG C/min.
Present invention also offers the sub-manganese-application of conductive black composite material in lithium ion battery negative of above-mentioned nanoscale.This materials application is in lithium ion battery negative, and after 50 circulations, capability retention is greater than 80%, at 500mA g
-1current charge-discharge electricity condition under, practical stability capacity (charge and discharge cycles more than 20 times) is greater than 450mAh g
-1.
Beneficial effect:
The invention provides the business-like cheap conductive black of a kind of employing as substrate, the manganous oxide nano particle of load high electrochemical activity is to obtain manganous oxide-conductive black composite material and synthetic method.Technical matters is simple, and raw material is environmentally friendly, and product has excellent electrochemistry performance as lithium ion battery negative material, is expected to the lithium ion battery negative material large-scale application of alternative current business-like graphite cathode as a new generation.
Accompanying drawing explanation
Fig. 1 is the electron microscope picture of the intermediate product manganese oxide/conductive black composite material of the embodiment of the present invention 1;
Fig. 2 is the electron microscope picture of the embodiment of the present invention 1 product manganous oxide/conductive black composite material;
Fig. 3 is the constant current charge-discharge curve of the embodiment of the present invention 1 product;
Fig. 4 is the embodiment of the present invention 1 product low range (100mA g
-1) under cycle performance of battery figure;
Fig. 5 is the embodiment of the present invention 1 product high magnification (1000mA g
-1) under cycle performance of battery figure;
Fig. 6 is the constant current charge-discharge curve of the embodiment of the present invention 2 product;
Fig. 7 is the embodiment of the present invention 2 product high magnification (500mA g
-1) under cycle performance of battery figure;
Fig. 8 is the XRD diffraction pattern of the embodiment of the present invention 3 product;
Fig. 9 is the embodiment of the present invention 3 product high magnification (500mA g
-1) under cycle performance of battery figure.
Embodiment
Method involved in the present invention comprises but is not limited to the material in following examples.
Embodiment 1: the preparation of manganous oxide/conductive black composite material and be assembled into the electrochemical property test of simulated battery with Li.
2g potassium permanganate (purchased from Shanghai Ling Feng chemical reagent Co., Ltd) is dissolved in 500mL deionized water, adds 1g conductive black (purchased from Shanghai jade of the He family company), abundant mixing and stirring.By gained mixed liquor at 60 DEG C of reaction 12h, filter, by the abundant washed product of deionized water, dry, the manganese oxide obtained/conductive black compound microscopic appearance is as Fig. 1.At hydrogen-argon-mixed (10%H in tube furnace
2, 90%Ar) the ramp to 400 DEG C of the lower 1 DEG C/min of atmosphere, insulation 5h, naturally cool to room temperature, namely obtain nano oxidized sub-manganese/conductive black composite material, as shown in Figure 2, the particle diameter of manganous oxide/conductive black compound is at 50nm-80nm for microstructure.
The sample that above-mentioned example 1 is prepared with PVDF according to 9:1 quality than Homogeneous phase mixing, take NMP as solvent, after mixing, be coated on 10 micron thickness Copper Foils.Beat sheet to be placed in 100 DEG C of vacuum drying chambers and to dry, obtain electrode slice.Be to electrode with metal lithium sheet, electrolyte uses 1M LiPF
6, in the glove box of argon shield, be assembled into simulated battery.Charge-discharge performance investigated by high accuracy battery tester.Record current density 100mA g
-1lower first charge-discharge curve as shown in Figure 3.The capacity after 20 times that circulated under this multiplying power by material is almost undamped, and after 20 circulations, capacity is 643mAh g
-1, (as shown in Figure 4) reaches business-like graphite cathode theoretical capacity (372mAh g
-1) nearly 2 times.(1000mA g under heavy-current discharge multiplying power
-1), after material circulation 75 times, capacity is 453mA g
-1, 83.4% of raw capacity can be maintained, there is good cyclical stability and large current density power (as shown in Figure 5).
Embodiment 2: the preparation of manganous oxide/conductive black composite material and be assembled into the electrochemical property test of simulated battery with Li.
4g potassium permanganate (purchased from Shanghai Ling Feng chemical reagent Co., Ltd) is dissolved in 500mL deionized water, adds 1g conductive black (purchased from Shanghai jade of the He family company), abundant mixing and stirring.By gained mixed liquor at 60 DEG C of reaction 16h, filter, by the abundant washed product of deionized water, dry.Hydrogen nitrogen mixed gas atmosphere (10%H in tube furnace
2, 90%N
2) under with the ramp to 500 DEG C of 2 DEG C/min, insulation 2h, naturally cool to room temperature, namely obtain nano oxidized sub-manganese/conductive black composite material; The particle diameter of the manganous oxide obtained/conductive black compound is at 50nm-80nm.This material is prepared as lithium ion battery negative, and charging and discharging curve as shown in Figure 6, can be found out, the specific capacity of material secondary electric discharge is 876mAh g
-1, after ten charge and discharge cycles, specific capacity does not only decay, and also slightly rise (907mAh g
-1), embody the cycle performance that material is good.Fig. 7 illustrative material is (500mA g under high current charge-discharge condition
-1), 50 capacity that circulate are almost undamped.
Embodiment 3: the preparation of manganous oxide/conductive black composite material and be assembled into the electrochemical property test of simulated battery with Li.
1g potassium permanganate (purchased from Shanghai Ling Feng chemical reagent Co., Ltd) is dissolved in 499mL deionized water, adds 1g conductive black (purchased from Shanghai jade of the He family company), abundant mixing and stirring.By gained mixed liquor at 80 DEG C of reaction 6h, filter, by the abundant washed product of deionized water, dry.In tube furnace under argon gas atmosphere with the ramp to 700 DEG C of 5 DEG C/min, insulation 2h, naturally cool to room temperature, namely obtain nano oxidized sub-manganese/conductive black composite material, the particle diameter of manganous oxide/conductive black compound is at 50nm-80nm; Its XRD diffraction image as shown in Figure 8, has good corresponding relation with JCPDS card No.78-0424MnO.By material with PVDF according to 9:1 quality than Homogeneous phase mixing, prepare lithium ion battery negative material, its 500mA g
-1as shown in Figure 9, after 20 circulations, capacity still reaches 489mAh g to cycle performance under current density
-1, and circulation volume is almost undamped.
Claims (6)
1. the sub-manganese-conductive black composite material of nanoscale, is characterized in that the mass ratio of manganous oxide and conductive carbon black in composite material is 0.5-2.5:1; Its primary particle size is 50nm-80nm.
2. synthesize a method for manganous oxide as claimed in claim 1-conductive black composite material, its concrete steps are as follows:
1) potassium permanganate and deionized water are made into liquor potassic permanganate, and are uniformly mixed homogeneous with conductive black, wherein the mass ratio of conductive black and potassium permanganate is 1:(1-4);
2) by above-mentioned steps 1) mixture that obtains reacts 6-16h at 60-80 DEG C, by product washing with dry, obtain manganese oxide-conductive black compound;
3) by above-mentioned steps 2) manganese oxide-conductive black compound of obtaining under reduction atmosphere or inert atmosphere, at 400-700 DEG C of roasting 2-5h, obtain the sub-manganese-conductive black composite material of nanoscale.
3. method according to claim 1, is characterized in that step 1) described in the mass concentration of liquor potassic permanganate be 0.2-0.8%.
4. method according to claim 1, is characterized in that step 3) described in protective atmosphere or the non-nitrogen of reducing atmosphere, argon gas, carbon dioxide, helium, ammonia, hydrogen, at least one in hydrogen-argon-mixed or hydrogen nitrogen mixed gas.
5. method according to claim 1, is characterized in that step 3) in heating rate 1-5 DEG C/min.
6. the sub-manganese-application of conductive black composite material in lithium ion battery negative of nanoscale as claimed in claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979545A (en) * | 2015-06-10 | 2015-10-14 | 苏州冷石纳米材料科技有限公司 | Flower-shaped manganese oxide microsphere material and preparation method and application thereof |
| CN106684332A (en) * | 2017-03-14 | 2017-05-17 | 西南大学 | Preparation method of lithium ion battery anode material with laminated structure |
| CN108273496A (en) * | 2018-03-16 | 2018-07-13 | 西南大学 | A kind of preparation method and applications of the bionic enzyme based on bacteria cellulose |
| CN112374552A (en) * | 2020-11-12 | 2021-02-19 | 昆明云大新能源有限公司 | Composite modified graphite negative electrode material and preparation method thereof |
| CN113150579A (en) * | 2021-03-24 | 2021-07-23 | 茂名环星新材料股份有限公司 | Method for removing impurities in carbon black and application thereof |
| CN114874433A (en) * | 2022-05-11 | 2022-08-09 | 四川大学 | Preparation method of manganous oxide doped isomelanin nano material and film with electromagnetic shielding function and product |
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| CN102810673A (en) * | 2012-08-16 | 2012-12-05 | 山东大学 | Method for preparing carbon-coated MnO coaxial nanowire cathode material for lithium ion batteries |
| CN102844913A (en) * | 2010-03-31 | 2012-12-26 | 日本贵弥功株式会社 | Composite of metal oxide nanoparticles and carbon, method for producing said composite, electrode using said composite, and electrochemical element |
| CN103311529A (en) * | 2013-06-17 | 2013-09-18 | 华东理工大学 | Legume-shaped carbon-coated manganese oxide core-shell structure composite material and preparation method and application thereof |
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2015
- 2015-01-22 CN CN201510032616.1A patent/CN104638257A/en active Pending
Patent Citations (3)
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| CN102844913A (en) * | 2010-03-31 | 2012-12-26 | 日本贵弥功株式会社 | Composite of metal oxide nanoparticles and carbon, method for producing said composite, electrode using said composite, and electrochemical element |
| CN102810673A (en) * | 2012-08-16 | 2012-12-05 | 山东大学 | Method for preparing carbon-coated MnO coaxial nanowire cathode material for lithium ion batteries |
| CN103311529A (en) * | 2013-06-17 | 2013-09-18 | 华东理工大学 | Legume-shaped carbon-coated manganese oxide core-shell structure composite material and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104979545A (en) * | 2015-06-10 | 2015-10-14 | 苏州冷石纳米材料科技有限公司 | Flower-shaped manganese oxide microsphere material and preparation method and application thereof |
| CN106684332A (en) * | 2017-03-14 | 2017-05-17 | 西南大学 | Preparation method of lithium ion battery anode material with laminated structure |
| CN108273496A (en) * | 2018-03-16 | 2018-07-13 | 西南大学 | A kind of preparation method and applications of the bionic enzyme based on bacteria cellulose |
| CN112374552A (en) * | 2020-11-12 | 2021-02-19 | 昆明云大新能源有限公司 | Composite modified graphite negative electrode material and preparation method thereof |
| CN113150579A (en) * | 2021-03-24 | 2021-07-23 | 茂名环星新材料股份有限公司 | Method for removing impurities in carbon black and application thereof |
| CN114874433A (en) * | 2022-05-11 | 2022-08-09 | 四川大学 | Preparation method of manganous oxide doped isomelanin nano material and film with electromagnetic shielding function and product |
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Application publication date: 20150520 |