CN108417820B - Graphene-aluminum ion super battery and preparation method thereof - Google Patents
Graphene-aluminum ion super battery and preparation method thereof Download PDFInfo
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- CN108417820B CN108417820B CN201810238281.2A CN201810238281A CN108417820B CN 108417820 B CN108417820 B CN 108417820B CN 201810238281 A CN201810238281 A CN 201810238281A CN 108417820 B CN108417820 B CN 108417820B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a graphene-aluminum ion super battery, which takes aluminum or aluminum alloy soaked by gallium indium tin eutectic alloy as a battery anode, takes graphene with a three-dimensional microporous structure as a battery cathode, and adopts (NH)2)2CO/AlCl3The ionic liquid is used as electrolyte. Meanwhile, the invention also discloses a preparation method of the graphene-aluminum ion super battery, and the method finally achieves the aim of industrially preparing the aluminum ion super battery with high capacity, high energy density, high power density, rapid charge and discharge (second charge and second discharge) and ultra-long stable charge and discharge cycle capacity (millions of times).
Description
Technical Field
The invention relates to a high-performance graphene-aluminum ion primary super battery which has the characteristics of high energy density and high power density and can be rapidly charged and discharged, and belongs to the application fields of electric automobiles, electromagnetic ejection, space technology, smart grids, distributed energy systems and the like.
Background
At present, the most successful battery cathode material for industrialization is graphite, but the theoretical capacity of the graphite is only 373mAh/g, and the requirements of the fields of electric automobiles, electromagnetic ejection, future space technology, smart grids, distributed energy systems and the like on batteries with high energy density and high power density are difficult to meet. The lithium ion battery is industrialized for more than twenty years, and the energy density of the commercial lithium ion battery can reach 100-150 Wh/kg, while the lead-acid and nickel-cadmium batteries are only 20-40 Wh/kg, and the nickel-metal hydride batteries are 50-70 Wh/kg; in terms of power density, the lithium ion battery can reach 1800W/kg. However, 1) when the discharge rate is large, the capacity of the lithium ion battery is greatly reduced, and the use requirements of electric vehicles, electromagnetic ejection and the like cannot be met; 2) lithium ion batteries present serious safety problems and, in the case of abuse or misuse, risk of explosion. At present, the aluminum ion battery with the rapid charging (1min rapid charging) performance is more stable in cycle charging and discharging (7500 cycles) than the lithium ion battery (100 cycles), and has no danger of explosion. However, since it uses a graphite sheet as a cathode material, both the energy density (40Wh/kg) and the power density (3000W/kg) are low. Due to the ultrahigh conductivity and the ultra-large specific surface area of the graphene, the theoretical energy storage capacity of the graphene is twice that of graphite and is as high as 744 mAh/g. Meanwhile, the ultrathin layered structure of the graphene and the nano-scale micropores on the surface of the ultrathin layered structure can effectively shorten the diffusion distance of ions, improve the diffusion rate of the ions, increase the electroactive sites of the electrode material, and facilitate the permeation of electrolyte and ion transportation, thereby improving the rate capability and the cycle performance of the ion battery.
Aluminum is a high-density energy carrier, the specific volume capacity of the aluminum is 8.10Ah/cm3, and the electrochemical equivalent is 2.98 Ah/g. In addition, the source of the metal aluminum is wide, the reserves are rich, the price is low, and the environment pollution is avoided. The above advantages make aluminum an ideal electrode material for developing batteries. Although there are many researches on aluminum batteries, the industrial industrialization of the aluminum batteries has not been really realized, and the three reasons are as follows: 1) the aluminum is easy to form a compact oxide film, so that the potential of an aluminum electrode is rapidly reduced; 2) aluminum is active and is easy to have severe hydrogen evolution reaction with a medium; 3) in alkaline media, aluminum anode flow and corrosion reactions produce Al (OH)3, which reduces electrolyte conductivity and increases aluminum anode polarization, deteriorating aluminum cell performance.
The Nature-Command article reports an aluminum ion cell utilizing natural graphite flakes as the cathode electrode, which performs well, reaching a capacitance of about 110mAh/g and a coulombic efficiency of about 98%. Under 6C multiplying power, the battery capacitance is 60mAh/g, and the coulombic efficiency is about 99% after more than 6000 charge-discharge cycles. In addition, the behavior mechanism of the chloroaluminate ions embedded in the graphite layer is researched through theoretical calculation simulation.
The report of the American academy of sciences reports that an aluminum ion battery using an aluminum chloride and urea ion liquid electrolyte has excellent coulombic efficiency which can reach 99.7%. Under the multiplying power of 1.4C, the battery capacity is 73mAh/g, and the battery can be stably charged and discharged for more than 200 times. The aluminum ion battery formed by the materials has low cost and excellent electrochemical performance, and the aluminum ion battery becomes an ideal power grid electricity storage system.
At present, aluminum ion batteries become a new research hotspot in the field of electrochemical energy storage batteries, and research teams of developed science and technology countries such as Europe, America, Japan, Korea, Australia and the like are engaged in relevant research works. In China, research teams including professor Lenmang of Shandong science and technology university, professor Lu Bian of Hunan university, professor Johnson of Beijing science and technology university, professor Gao superior of Zhejiang university, professor Ouyangchu of Jiangxi university and the like also successively published several research papers about graphite as a cathode material after 2015. These efforts further push aluminum ion batteries toward practical use.
In terms of industrialization process, AB Systems INC of silicon valley creative company has been exclusively granted by Stanford university aluminum ion battery patent (patent application date: 1st US technical filed on Feb 28, 2014; 2nd US technical filed on Nov 6, 2014; PCT application filed on Feb 27, 2015). At present, the company has successfully gathered the dominant resources of various units produced, learned, researched and used at home and abroad, and the aluminum ion battery is pushed to the market to be applied.
A high-polymer science and engineering department high super professor team at Zhejiang university designs and prepares the graphene film cathode material, and an aluminum-graphene battery with ultrahigh multiplying power and ultralong cycle performance is obtained. The specific capacity of the graphene anode reaches 120mAh g-1, and 91% of capacity can be still maintained after 250,000 cycles; meanwhile, the material has excellent rate performance, and still has the reversible specific capacity of 111mAh g-1 under the current density of the highest 400Ag-1 (3333C, full charge in 1.1 seconds). The aluminum-graphene battery can work at-40 to 120 ℃, and stable circulation of 1000 circles and 45,000 circles is realized at-30 ℃ and 100 ℃. This wide temperature use range lays the foundation for the use of aluminum ion batteries under extreme temperature conditions in the future. Meanwhile, the flexible and safe paper has better flexibility and safety, and the capacity is completely maintained after 10,000 times of bending; the battery cell does not catch fire or explode even when exposed to flame, and shows application potential in wearable flexible electronic devices. The rate capability and cycle life of the battery far exceed those of other battery materials, and the aluminum-graphene super battery with higher energy density and equivalent rate capability and cycle life compared with a super capacitor can be realized.
The achievement of this result also benefits from the prior accumulation of the senior team and the learning reference to the former work. In the field of aluminum-graphene batteries, a superordinate team provides a defect-free design principle (adv. Mater.2016, 29, 1605958; adv. EnergyMater.2017, 7, 1700051) of a positive graphene material, discovers a dendritic phenomenon and an inhibition mechanism (ACS appl. Mater. & Inter., 2017, 9, 22628) of an aluminum negative electrode, and designs and prepares a high-flexibility high-thermal-conductivity graphene assembly film (adv. Mater.2017, 29, 1700589).
In the field of aluminum ion battery research, professor davidia of stanford university has made pioneering work, and first, an aluminum ion battery with high specific capacity and long cycle is realized (Nature, 2015, 520, 324). Earlier, professor of traditional Chinese science proposed a 'three-continuous' design concept of electrode material (adv. mater.2016, 28, 2409) in the study of sodium-ion batteries, and realized an ultrafast long-cycle sodium-ion battery.
Professor los angeles school division pioneer, california university in usa (Science, 2017, 5.12) reported that they developed a porous graphene composite electrode technology, and the development of a battery with high charging speed and high endurance is an important step. The charging speed is determined by the power density, and the service life is determined by the energy density, but for most of the current batteries, increasing the power density and increasing the energy density usually conflict with each other. The composite electrode which is prepared by taking the porous graphene as a three-dimensional frame structure and uniformly growing the nano-particle niobium pentoxide on the surface can simultaneously realize two aims of quick charging and long service life. Nanoelectrode materials theoretically have very high energy or power densities, but have been difficult to commercialize because their loading is difficult to increase, typically 10 times less than the areal density of the active material commonly used in commercial energy storage devices. If the thickness of the electrode material is increased, the diffusion resistance of ions is significantly increased, resulting in a sharp drop in the performance of the electrode. Therefore, the area capacity or area current density of the final energy storage device is difficult to exceed the level of the existing lithium ion battery.
At present, the research of the aluminum ion battery does not reach the performance indexes of the lithium battery or other types of batteries, and the main problems are low battery discharge voltage, capacitance performance without a discharge voltage platform, low energy density, low power density and the like. The Stanford university aluminum ion battery adopts the graphite sheet as a cathode material, has the highest voltage (about 2V) and the energy density of 40Wh/kg in the similar material batteries, and has a great difference compared with the common rated voltage of a lithium battery which is more than 3V and the power density of 130-150 Wh/kg. However, both the energy density (40Wh/kg) and the power density (3000W/kg) were low.
The main factors that limit the development of aluminum anodes for aluminum ion batteries are: 1) the aluminum is easy to form a compact oxide film, so that the potential of an aluminum electrode is rapidly reduced; 2) aluminum is active and is easy to have severe hydrogen evolution reaction with a medium; 3) in alkaline media, aluminum anode flow and corrosion reactions produce Al (OH)3, which reduces electrolyte conductivity and increases aluminum anode polarization, deteriorating aluminum cell performance.
The limitation of graphene electrode applications is mainly due to the different preparation methods that result in different properties of graphene. The ionic liquid is easy to form a passivation film on the surface of the graphene negative electrode, so that the irreversible specific capacity loss of the graphene negative electrode in the first charge-discharge process reaches 30-50%, and the structure and configuration of the graphene are important for improving the electrochemical properties of the electrode material. The graphene is used for the cathode of the aluminum ion battery and has the necessary requirements of being composed of single-layer graphene, having a mesoporous structure distribution, having small-size and proper lattice defects, having a definite arrangement order and being in close contact with each other. The aluminum ion battery has high specific capacity, high working voltage, large specific power and long cycle life. Other factors that limit the application of graphene electrodes include: the technical scheme of graphene as an electrode has not been effectively studied. At present, the battery electrode scheme of the university of california los angeles is explored after high-capacity nano materials such as nano silicon, sulfur and the like are compounded with porous graphene, and the graphene is actually mainly used as a carrier and is a nano Nb2O5 electrode so that the mass ratio discharge capacity is improved, and the graphene is not really used as an electrode material; in the absence of an effective preparation method for preparing high-quality graphene on a large scale, firstly, the mechanical stripping method can obtain high-quality graphene, but the yield is too low, the size and the thickness are not easy to control, and the high-quality graphene cannot be prepared on a large scale. Secondly, the chemical oxidation-reduction method has low cost and high yield, but the prepared graphene has defects of different degrees in structure. Thirdly, performing secondary filtration; the chemical vapor deposition method can obtain high-quality graphene films, but is limited by the currently used equipment and graphene transfer method, and large-area graphene films cannot be prepared and produced in a large scale. Therefore, how to prepare high-quality graphene in a large scale also becomes a key factor for restricting the application of graphene in high-performance ion batteries and the industrialization of graphene batteries.
Disclosure of Invention
In order to solve the problems, the invention takes a three-dimensional porous graphene electrode as a cathode and takes urea-alumina ionic liquid ((NH)2)2CO/AlCl3Type ionic liquid) is used as electrolyte, aluminum or aluminum alloy infiltrated by gallium indium tin eutectic alloy with low melting point is innovatively used as an anode, and the graphene-aluminum ion super battery which has the advantages of high capacity, ultrahigh power density, high energy density, high coulombic efficiency, more stable cyclic charge and discharge and quick charge and discharge is provided.
The invention provides
The invention has the beneficial effects that:
(1) the invention provides a method for preparing a high-performance graphene-aluminum ion super battery which can be applied to the future electric automobile, electromagnetic ejection and other leading-edge application fields. The method combines the large-scale industrial production process of high-quality graphene powder and three-dimensional porous graphene electrodes, adopts the preparation technology of aluminum or aluminum alloy anode materials soaked by gallium-indium-tin eutectic alloy and high-performance ionic liquid electrolyte, and finally achieves the aim of preparing the graphene-aluminum ion super battery with high capacity, high energy density, ultrahigh power (megawatt/kg), rapid charge and discharge (second charge and second discharge), high coulombic efficiency (95%) and ultra-long stable charge and discharge cycle capacity (millions of times).
(2) Graphene-aluminum ion super cell: the energy density is more than or equal to 300Wh/kg, the power density reaches the megawatt/kg level, the coulombic efficiency is more than or equal to 95 percent, the rapid charging is less than or equal to 9s, and the battery efficiency is more than or equal to 90 percent after millions of charging and discharging cycles.
(3) According to different application fields, the power density of the battery can be regulated and controlled within a large range, the highest energy density can reach 27.5 × 104W/kg, which is 90 degrees times that of an aluminum ion battery developed by the most advanced American stanford university in the world, and the energy density is about 76Wh/kg and about 2 times that of the aluminum ion battery2)2CO/AlCl3The ionic liquid is used as an electrolyte, which can effectively inhibit the hydrogen evolution reaction of the anode, effectively improve the quality of deposited aluminum and improve the reversibility of the electrode, so that the battery also has super-long stable charge-discharge cycle capacity. The three-dimensional microporous structure graphene prepared by the method is used as a battery cathode, and the capacity, the energy density, the power density, the rate capability and the cycling stability of the battery can be greatly improved. In the process of rapid charge and discharge, the device has a higher discharge platform. This scheme supports reversible deposition and dissolution of aluminum at the anode and reversible intercalation and deintercalation of ions at the anode.
(4) In order to greatly improve the electrochemistry of the aluminum batteryThe invention 1) adopts aluminum or aluminum alloy soaked by gallium indium tin eutectic alloy with low melting point as the anode of the battery, which can destroy the compact oxide film on the surface of the aluminum, improve the activity of the aluminum electrode and improve the multiplying power performance of the battery; 2) by (NH)2)2CO/AlCl3The ionic liquid is used as electrolyte, which can effectively inhibit the hydrogen evolution reaction of the anode, effectively improve the quality of deposited aluminum and improve the reversibility of the electrode; 3) the graphene with the three-dimensional microporous structure is used as the cathode of the battery, so that the capacity, the energy density, the power density, the rate capability and the cycling stability of the battery can be greatly improved.
(5) The unique electronic structure and the special layered nano microporous structure of the graphene enable the graphene to have ultrahigh conductivity and ultrahigh specific surface area, provide an excellent conveying channel for the permeation of electrolyte and the transmission of electrons and ions, enable the graphene to become an optimal electrode material of a high-performance energy storage system, and exert huge application value in the field of energy sources.
(6) The invention also adopts a scheme of preparing the graphene electrode with the three-dimensional microporous structure by self-assembly to solve the problems, and simultaneously utilizes the three-dimensional micron pore channel structure and the aerogel three-dimensional cross-linking structure of the graphene to improve the utilization efficiency of the electrode, provide a transfer channel of ions, ensure the transmission mode of electrolyte ions in a three-dimensional space, be beneficial to the full exertion of capacitive energy, greatly improve the capacity, energy density, power density and circulation stability of the battery, and simultaneously solve the problem of low discharge voltage of the aluminum battery.
(7) The present invention adopts (NH)2)2CO/AlCl3The ionic liquid is used as electrolyte, so that the hydrogen evolution reaction of the anode can be effectively inhibited, the quality of deposited aluminum is improved, and the reversibility of the electrode is improved; the aluminum or aluminum alloy infiltrated by the gallium indium tin eutectic alloy is used as the anode of the battery, so that the compact oxide film on the surface of the aluminum can be damaged, the activity of the aluminum electrode can be improved, and the rate capability of the battery can be improved. Therefore, the graphene-aluminum ion battery has the advantages of high capacity, high energy density, super-high power, rapid charge and discharge, high coulombic efficiency and super-long charge and dischargeAnd (4) cycling stability.
Drawings
FIG. 1 is a microstructure diagram of a graphene electrode material with a three-dimensional microporous structure;
fig. 2 is a graph comparing performance of graphene batteries with other energy devices;
fig. 3 is a schematic diagram of charging and discharging of a graphene-aluminum ion battery;
fig. 4 is a graph of graphene-aluminum ion battery performance;
fig. 5 is a graph of graphene-aluminum ion battery energy efficiency and power density;
FIG. 6 low melting point liquid metal gallium-aluminum phase diagram;
FIG. 7 is a flow chart of graphene powder preparation;
FIG. 8 is a schematic diagram of self-assembly preparation of graphene with a three-dimensional structure;
FIG. 9 is a schematic diagram of a three-dimensional microporous graphene CVD method;
Detailed Description
The technical scheme of the invention is explained in detail in the following with reference to the attached drawings 1-9.
Example 1:
this example provides a graphene-aluminum ion super cell, in which aluminum or an aluminum alloy infiltrated with a gallium indium tin eutectic alloy with a low melting point is used as a cell anode, graphene with a three-dimensional microporous structure is used as a cell cathode (as shown in fig. 1), and (NH) is used2)2CO/AlCl3The ionic liquid is used as electrolyte. The graphene battery and other energy device performance pairs are shown in fig. 2.
The charge-discharge chemical reaction principle of the graphene-aluminum ion super battery is as follows:
on the anode side, the metals Al and AlCl4Oxidation-reduction reaction to Al2Cl7-and outputting the charge from the external circuit;
at the cathode side, AlCl embedded between graphene layers4-release into the electrolyte.
The battery charging process is the reverse process of the above reaction, and the redox reaction equation is shown as the following formula:
in which n represents a C atom and an intercalated anionic AlCl4-molar ratio between. The charge and discharge principle of the graphene-aluminum ion battery is shown in fig. 3.
Through deep theoretical analysis and systematic experimental verification, the graphene-aluminum ion super battery described in the embodiment can finally and effectively solve the problems of the common aluminum battery, namely:
1) the potential of the aluminum electrode is rapidly reduced due to the formation of the oxide film;
2) the aluminum electrode has serious hydrogen evolution reaction;
3) the aluminum anode polarization causes the reversibility of the aluminum electrode to be reduced and the like. And the energy storage capacity, the power density, the coulombic efficiency, the charge-discharge cycle stability and the rapid charge-discharge capacity of the aluminum battery can be greatly improved.
Meanwhile, according to the charge and discharge processes, the number of layers, the interlayer spacing, the specific surface area and the micropore size of the graphene with the three-dimensional structure of the cathode directly influence the embedding amount and the embedding and de-embedding rates of the anion AlCl 4-on the graphene electrode, so that the energy storage capacity, the power density, the charge and discharge speed, the coulombic efficiency and the cyclic charge and discharge stability of the battery are directly influenced. Therefore, the quality of the graphene electrode structure directly influences various electrochemical performances of the battery to a great extent.
This example provides a graphene-aluminum ion super cell with aluminum or aluminum alloy infiltrated with a gallium indium tin eutectic alloy as the anode, a three-dimensional porous graphene electrode as the cathode, and (NH) as the cathode2)2CO/AlCl3The graphene-aluminum ion battery is prepared by taking the type ionic liquid as electrolyte, various electrochemical performances of the battery are tested and characterized by adopting a cyclic voltammetry method and a constant-current charging and discharging method, and the experimental results obtained at present find that:
the prepared graphene electrode has a stable three-dimensional porous structure and a large specific surface area, so that rapid diffusion and sufficient contact reaction of aluminum ion liquid in the graphene electrode can be realized, and rapid charging and discharging can be realized.
As shown in fig. 4a), when the charging current density was 15000mA/g, the battery efficiency was maintained at 90% or more, and the capacity was maintained at 85% or more. As shown in fig. 4b), the battery can realize fast charging and slow discharging, and the discharge time of 0 is 3283 seconds which is more than 170 times of the discharge time when the charging time is 19 seconds.
As shown in fig. 4c), the discharge capacity can still be maintained at about 20mAh/g when one charge-discharge cycle time is reduced to 1.2 seconds. As shown in fig. 4d), the battery also has a higher discharge plateau, and thus the battery has a higher energy density and power density, as shown in fig. 5. Meanwhile, the aluminum or aluminum alloy soaked by the gallium indium tin eutectic alloy with low melting point is used as the battery anode, and the ionic liquid is used as the electrolyte, so that the hydrogen evolution reaction of the aluminum electrode in the charging and discharging process of the battery can be effectively inhibited, the reversibility of the aluminum electrode is improved, and the battery also has ultralong stable charging and discharging cycle capacity.
Example 2
The embodiment provides a graphene-aluminum ion super battery manufacturing method;
Step 1.1, soaking the aluminum wire in a mixed solution composed of concentrated sulfuric acid, nitric acid and phosphoric acid to remove an oxide layer on the surface.
And 1.2, repeatedly washing the aluminum by deionized water to remove aluminum compounds generated on the surface and residual acid.
And 1.3, completely immersing the aluminum wire in the gallium-indium-tin eutectic alloy in a sealed container, vacuumizing, filling argon, keeping the container in an oxygen-free and water-free state, and standing for a period of time to obtain the battery anode.
In the step, the liquid metal is an alloy consisting of gallium, indium and tin, the mass ratio of the gallium to the indium to the tin is 68:12:20, and the melting point is 12.7 ℃. Wherein, gallium and aluminum are mutually soluble, and the forms of aluminum and gallium in the mixture are different according to different proportions, as shown in fig. 6.
As can be seen from the figure: when the gallium indium tin eutectic alloy and the aluminum interact, part of the aluminum is fused into the liquid metal and exists in the form of nano aluminum particles or atomic aluminum. The nanoscale aluminum particles and aluminum atoms have higher reactivity than solid aluminum.
And step 1.4, soaking for 0.5-48 hours to realize the optimal penetration of the gallium indium tin eutectic alloy with low melting point.
When the aluminum-liquid metal prepared according to the steps is used as a battery anode material, the aluminum-liquid metal has the following characteristics:
1) the lithium ion battery can quickly participate in chemical reactions generated in the charging and discharging processes of the battery, so that the battery has higher rate capability;
2) due to the characteristic that liquid metal and aluminum are mutually soluble, the problems that metal dendrite is formed in the process of rapid charging and discharging of the battery, the reversibility of an electrode is influenced, the performance of the battery is reduced, the service life of the battery is shortened and the like can be solved;
3) the passive film with stable surface property and compact structure of the aluminum is destroyed, and the activity of the aluminum electrode is improved;
4) the constructed battery has the advantages of high safety, quick charge and discharge, good cycle performance and the like.
And 2, preparing graphene powder, namely blending graphite with o-dichlorobenzene, N-methyl pyrrolidone, dimethylformamide, ionic liquid and the like, then carrying out ball milling, using ultrasonic treatment as assistance, and then treating impurities generated in the ball milling process by using dilute acid to obtain the graphene with complete morphology and structure.
The ionic liquid can be selected from various imidazole ionic liquid lubricants.
In the preparation process of the method, oxidation-reduction reaction does not exist, the obtained graphene has no structural defects and is not oxidized, and the complete morphology and performance of the graphene can be maintained.
Selecting dry ice as a substitute for o-dichlorobenzene, N-methyl pyrrolidone, dimethylformamide and ionic liquid, and performing ball milling to obtain edge carboxylated graphene oxide capable of realizing self-stripping in a solution; in the preparation process, carboxyl is only concentrated on the edge of graphene without damaging an sp2 area in a graphene sheet, and then hydrazine hydrate, sodium borohydride, hydroquinone, alcohols, urea and ascorbic acid are used as reducing agents to prepare graphene powder by combining high-temperature heat treatment reduction.
The method is low in cost, simple in process flow and equipment, and the obtained graphene is complete in shape and structure, so that the method is suitable for large-scale continuous industrial production of high-quality graphene powder.
The specific preparation flow chart is shown in the following figures 7-8:
step 3, preparing the graphene electrode with the three-dimensional microporous structure by self-assembly
Self-assembly preparation of the graphene with the three-dimensional microporous structure is carried out by utilizing self-made high-quality graphene powder and adopting an emulsion template method. The preparation process comprises the following steps:
and 3.1, fully mixing the graphene solution with an organic solvent, and emulsifying to obtain a graphene dispersion liquid, wherein in the embodiment, the organic solvent can be n-hexane, and the n-hexane is uniformly dispersed in the graphene solution in the form of droplets of about 200 micrometers.
And 3.2, carrying out hydrothermal treatment, wherein the graphene sheets are mutually lapped around the microdroplets to form gel in the process. And putting the graphene gel into warm water, evaporating the organic solvent in the gel and completely filling the graphene micropores with water.
And 3.3, quickly freezing the graphene in liquid nitrogen, and freeze-drying to obtain the three-dimensional graphene with the micron pore size.
The preparation principle is schematically shown in the following figure 9:
in an alternative embodiment, a CVD method can also be used for growing the graphene electrode with the three-dimensional microporous structure
The CVD method is simple and easy to prepare the graphene, the obtained graphene has high quality, can realize large-area preparation, is easy to transfer to various substrates, and is a main method for preparing high-quality graphene films.
The CVD method is to use carbon-containing compounds (such as methane, acetylene, etc.) as carbon sources at high temperature (such as 1000 ℃), and to decompose the gases on the surface of a metal substrate by passing the gases through the metal substrate, thereby growing high-quality graphene. The schematic diagram of a common CVD apparatus is shown in FIG. 7:
the common CVD method for preparing graphene uses metal sheets (copper, nickel, etc.) as substrates, and the grown graphene is a layered thin film structure.
In order to directly grow the graphene with the three-dimensional structure, three-dimensional reticular metal nickel is used as a template, and the graphene is directly grown on the surface of the reticular nickel in a methane atmosphere at 1000 ℃; then, coating polymethyl methacrylate (PMMA) on the surface of the graphene-nickel compound, and placing the graphene-nickel compound in a nickel etching solution to etch away metallic nickel; and finally, washing PMMA in acetone to obtain the graphene with the three-dimensional microporous structure.
The invention also provides a large-scale production technology for preparing the three-dimensional graphene by the CVD method, and provides a technical method for continuously producing the graphene in a roll-to-roll mode. Meanwhile, a roll-to-roll coating technology is adopted to etch metal nickel or copper and transfer graphene at a later stage, so that large-scale industrial production of the graphene with the three-dimensional structure is realized.
Step 4, preparing aluminum ion liquid electrolyte
Aluminum is very active in nature and cannot undergo a reversible reaction of precipitation and dissolution in an aqueous electrolyte. The ionic liquid has the excellent characteristics of good thermal stability, wide electrochemical window (up to 5V), high conductivity, good solubility and the like, and can be used as an electrolyte of a high-performance battery.
Among the numerous ionic liquids, (NH)2)2CO/AlCl3The ionic liquid has higher conductivity, wider potential window and melting point close to room temperature, is economical and easy to obtain, can obtain a target product through one-step reaction, and can obtain the target product by adjusting organic salt and AlCl3The acidity of the alloy can be adjusted to obtain a composition containing Al2Cl7-an ionic liquid. It can realize the dissolution and deposition of aluminum, effectively improve the quality of deposited aluminum and improve the electricityThe polarity is reversible, so that the electrolyte is suitable for being used as an electrolyte of an aluminum battery.
In the invention, (NH) is prepared by taking ionic liquid urea as a raw material2)2CO/AlCl3The ionic liquid specifically comprises the following components:
step 4, completing the preparation of the aluminum ion liquid electrolyte;
step 4.1, baking AlCl in high-temperature vacuum environment3To remove residual moisture contained therein;
step 4.2, in argon atmosphere, according to molar ratio (NH)2)2CO：AlCl3Is 1: 1.5 weighing dried urea and anhydrous aluminum trichloride, mixing and stirring the dried urea and the anhydrous aluminum trichloride until a product is non-viscous slurry, moving the slurry into a magnetic stirrer at the temperature of 55 ℃, synthesizing light yellow and transparent ionic liquid at the rotation speed of 550r/min, and if the obtained product contains non-dissolved impurities, centrifuging the product in a centrifuge;
step 4.3, drying in a vacuum drying oven at 60 ℃ for 24 hours, adding 0.05mmol/L benzoic acid into the dried ionic liquid, stirring until the ionic liquid is completely dissolved, and then placing in an environment with water and oxygen content less than 1ppm to obtain (NH)2)2CO/AlCl3And (3) an electrolyte. In the step, an additive is added after the ionic liquid is mixed, and one or more of benzoic acid, potassium chloride, choline chloride and tetramethylammonium chloride are used as the additive, wherein the addition amount is 0.05 mmol/L.
The graphene-aluminum ion super battery and the manufacturing method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the core concepts of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. A graphene-aluminum ion super battery is characterized in that: the low melting point of gallium indium tin is usedThe aluminum or aluminum alloy soaked by the melt alloy is used as a battery anode, the mass ratio of gallium, indium and tin in the gallium-indium-tin low-melting-point eutectic alloy is 68:12:20, the melting point is 12.7 ℃, the graphene with the three-dimensional microporous structure is used as a battery cathode, and (NH) is adopted2)2CO/AlCl3The ionic liquid is used as battery electrolyte; wherein: the graphene-aluminum ion super battery is prepared by the following steps:
step 1, preparing a gallium indium tin eutectic alloy with a low melting point, so that after the surface of aluminum is infiltrated, part of aluminum can be fused into the eutectic alloy and exists in the form of nano aluminum particles or atomic aluminum to be used as an anode electrode of a graphene-aluminum ion super battery;
step 1.1, soaking aluminum in a mixed solution composed of concentrated sulfuric acid, nitric acid and phosphoric acid to remove an oxide layer on the surface;
step 1.2, repeatedly washing aluminum by deionized water to remove aluminum compounds and residual acid generated on the surface;
step 1.3, completely immersing aluminum in the gallium-indium-tin eutectic alloy with low melting point in a sealed container, vacuumizing, then filling argon, keeping the container in an oxygen-free and water-free state, and standing for a period of time to be used as a battery anode;
step 1.4, soaking for 0.5-48 hours to realize the permeation amount of the gallium indium tin eutectic alloy with low melting point;
step 2, preparing graphene powder, namely blending graphite with o-dichlorobenzene, N-methyl pyrrolidone, dimethylformamide and ionic liquid, then performing ball milling, using ultrasonic treatment as assistance, and then removing impurities generated in the ball milling process through dilute acid to obtain graphene;
step 3, preparing a graphene electrode with a three-dimensional microporous structure by self-assembly;
step 3.1, fully mixing the graphene solution with an organic solvent, and emulsifying to obtain a graphene dispersion liquid;
step 3.2, carrying out hydrothermal treatment, wherein the graphene sheets are mutually lapped around the microdroplets to form gel in the process; putting the graphene gel into warm water, evaporating the organic solvent in the gel and completely filling the graphene micropores with water;
3.3, quickly freezing the graphene in liquid nitrogen, and obtaining the three-dimensional graphene with micron pore size after freeze drying;
step 4, completing the preparation of the aluminum ion liquid electrolyte;
step 4.1, baking AlCl in high-temperature vacuum environment3To remove residual moisture contained therein;
step 4.2, in argon atmosphere, according to molar ratio (NH)2)2CO：AlCl3Is 1: 1.5 weighing dried urea and anhydrous aluminum trichloride, mixing and stirring the dried urea and the anhydrous aluminum trichloride until a product is non-viscous slurry, moving the slurry into a magnetic stirrer at the temperature of 55 ℃, synthesizing light yellow and transparent liquid at the rotation speed of 550r/min, and if the obtained product contains non-dissolved impurities, centrifuging the product in a centrifuge;
step 4.3, drying in a vacuum drying oven at 60 ℃ for 24 hours, adding 0.05mmol/L benzoic acid into the dried ionic liquid, stirring until the ionic liquid is completely dissolved, and then placing in an environment with water and oxygen content less than 1ppm to obtain (NH)2)2CO/AlCl3And (3) an electrolyte.
2. The graphene-aluminum ion super cell according to claim 1, wherein the eutectic alloy of gallium indium tin low melting point penetrates into the matrix of aluminum or aluminum alloy, and mutual solution reaction occurs to form eutectic alloy of gallium indium tin and partial aluminum, and nano aluminum particles or atomic aluminum are attached around the anode to prevent the formation of aluminum oxide film, so that the cell reaction continues.
3. The graphene-aluminum ion super battery according to claim 1, wherein the cathode is selected from three-dimensional microporous graphene without structural defects and with intact morphology and performance.
4. The graphene-aluminum ion super battery according to claim 1, wherein in step 2, no redox reaction process exists, and graphene powder with complete morphology and structure is prepared.
5. The graphene-aluminum ion super battery according to claim 1, wherein in step 2, dry ice is selected as a substitute for o-dichlorobenzene, N-methylpyrrolidone, dimethylformamide and ionic liquid, and after ball milling, edge carboxylated graphene oxide capable of self-exfoliation in solution can be obtained; in the preparation process, carboxyl is only concentrated on the edge of graphene without damaging an sp2 area in a graphene sheet, and then hydrazine hydrate, sodium borohydride, hydroquinone, alcohols, urea and ascorbic acid are used as reducing agents to prepare graphene powder by combining high-temperature heat treatment reduction.
6. The graphene-aluminum ion super battery according to claim 1, wherein in step 3.1, the organic solvent is n-hexane, and the n-hexane is uniformly dispersed in the graphene solution as droplets with the diameter of 200 microns; and (4) selecting liquid nitrogen to freeze and dry the evaporated gel.
7. The graphene-aluminum ion super battery according to claim 1, wherein the battery electrolyte is selected from (NH)2)2CO/AlCl3Type ionic liquid of (NH)2)2CO and AlCl31: 1.5, one or more of benzoic acid, potassium chloride, choline chloride and tetramethylammonium chloride are mixed as additives, and the addition amount is 0.05 mmol/L.
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| WO2020056514A1 (en) * | 2018-09-19 | 2020-03-26 | The Governing Council Of The University Of Toronto | Aluminum-ion battery using aluminum chloride/amide-based deep eutectic solvents |
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| CN111261946B (en) * | 2018-11-30 | 2021-08-06 | 浙江大学 | Aluminum ion battery electrolyte solution and battery |
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| CN110098001B (en) * | 2019-05-29 | 2020-10-02 | 腾飞科技股份有限公司 | Flexible conductive wire body and forming process thereof |
| CN110683977B (en) * | 2019-09-10 | 2021-04-16 | 山东大学 | Aluminum ion battery electrolyte, preparation method and application |
| CN111204829B (en) * | 2020-01-07 | 2022-04-26 | 东南大学 | Solar sewage purification aerogel based on waste paper and graphite and preparation method thereof |
| CN112002937A (en) * | 2020-08-07 | 2020-11-27 | 山东科技大学 | Gel electrolyte for aluminum ion battery and preparation method and application thereof |
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