CN109950640B - Metal graphite medium temperature energy storage battery and preparation method thereof - Google Patents
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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
-
- 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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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了金属石墨中温储能电池及其制备方法，金属石墨中温储能电池，其特征在于，包括正极、负极和电解质，所述正极和负极之间设置有垫圈，电解质设置在垫圈中，其中，正极为石墨类材料；电解质为饱和YCl的YAlCl4，其中，Y为Li、Na或K；负极为X|XCl2固相复合电极，其中X为电负性高于Al的金属。电池运行温度为100℃～200℃，循环寿命超过10000次、平衡电压约为1～1.7V。
The invention discloses a metal-graphite medium-temperature energy storage battery and a preparation method thereof. The metal-graphite medium-temperature energy storage battery is characterized in that it comprises a positive electrode, a negative electrode and an electrolyte, a gasket is arranged between the positive electrode and the negative electrode, and the electrolyte is arranged in the gasket, The positive electrode is a graphite material; the electrolyte is YAlCl 4 saturated with YCl, where Y is Li, Na or K; the negative electrode is an X|XCl 2 solid-phase composite electrode, where X is a metal with higher electronegativity than Al. The operating temperature of the battery is 100℃～200℃, the cycle life is over 10,000 times, and the balance voltage is about 1～1.7V.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage batteries, and particularly relates to a metal graphite medium-temperature energy storage battery and a preparation method thereof.
Background
After the economy of China experiences extensive rapid growth period of large-scale resource investment, capacity removal and structure adjustment become key contents of the intensive development mode of the economic transformation of China at the present stage. The energy problem is the most critical problem in numerous economic development fields, the main content of the energy problem is to eliminate laggard and low-efficiency energy output, the utilization efficiency of the existing energy output is improved, renewable energy sources such as wind energy, solar energy and the like are vigorously developed, a smart grid is constructed to solve the problems of distribution regulation and control and efficient utilization of electric energy and the like, and the energy problems all provide higher requirements for large-scale energy storage technology. The energy storage technology is applied to the power system, so that the user demand side management can be effectively realized, the day and night peak-valley difference and the smooth load are reduced, the power supply cost is reduced, the utilization rate of renewable energy sources such as wind energy and solar energy can be promoted, the running stability of a power grid system is improved, the power quality of the power grid is improved, and the power supply reliability is ensured.
Common power energy storage technologies include pumped storage, compressed air energy storage, superconducting magnetic energy storage, super capacitor energy storage, flywheel energy storage, battery energy storage, and the like. The battery energy storage has become the first choice of large-scale energy storage technology in the future smart grid due to the advantages of low requirements on environment and space, high energy conversion efficiency, relatively low cost and the like. At present, several mainstream battery technologies for energy storage include lead-acid batteries, sodium-sulfur batteries, all-vanadium redox flow batteries, lithium ion batteries, and the like. The lead-acid battery has low energy density, low charge and discharge speed, short cycle life and great environmental pollution; the sodium-sulfur battery adopts the beta-alumina solid electrolyte, so that the manufacturing cost is high, the thermal stability is poor, and the sodium-sulfur battery is easy to crack to cause serious safety accidents; the flow battery also faces the technical problems of the electrolyte, electrode plates, particularly the ion exchange membrane and other key materials and the problem of higher energy storage price; the main limiting factor of lithium ion batteries in the energy storage market is that the cost of single energy storage in the whole life cycle is too high (about 0.12$ · kWh-1), which is difficult to be accepted by the commercial energy storage market. These limit to some extent the application of the above-mentioned battery technology to the energy storage of the power grid. Therefore, the development of novel low-cost battery technology suitable for the commercialized large-scale power grid energy storage market is urgent.
Disclosure of Invention
In order to solve the problems, the invention provides a metal graphite medium-temperature energy storage battery which is low in cost and suitable for a large-scale battery energy storage market and a preparation method thereof.
In order to achieve the purpose, the metal graphite medium-temperature energy storage battery comprises a positive electrode, a negative electrode and an electrolyte; the positive electrode is made of graphite materials; YAlCl with saturated YCl as electrolyte4The Y is Li, Na or K; the negative electrode is X | XCl2And the X is a metal with electronegativity higher than that of Al.
Further, the graphite material includes graphite, graphene, carbon nanotubes, graphite felt or carbon felt material.
Further, an electrolyte is disposed in the receiving gasket.
Further, the battery also comprises a shell used for accommodating the positive electrode, the negative electrode, the electrolyte and the gasket.
A preparation method of a metal graphite medium-temperature energy storage battery comprises the following steps:
step 1, preparing a negative electrode: preparing an X | XCl2 solid-phase composite electrode, wherein X is a metal with electronegativity higher than Al; preparing an electrolyte: mixing YCl with AlCl3Mixing to obtain electrolyte; and Y is Li or Na or K or a mixture of Li, Na and K in any proportion.
and 3, packaging the product prepared in the step 2 in a shell.
Further, in step 1, the X | XCl2 solid-phase composite electrode is prepared by the following three methods:
1) putting metal X into a container filled with HCl gas, drying and weighing the corroded X electrode after the corrosion is finished, and comparing the mass difference of the electrode before and after the corrosion to obtain X | XCl2Mass of Cl element in the solid phase composite electrode, thereby obtaining active XCl2The quality of (c).
2) Corroding the X electrode by hydrochloric acid with known concentration to enable the surface of the X electrode to be uniformly soaked with a layer of hydrochloric acid and to be completely reacted, and then drying the X electrode; comparing the electrode quality difference before and after corrosion to obtain X | XCl2The mass of Cl element in the solid phase composite electrode can be known, so that the activity XCl is known2And (4) quality.
3) Mixing X powder with XCl2Mixing the powders, wherein X powder and XCl powder2The mol ratio of the powder is (2-3): 1, sintering under the atmosphere of gas protection to prepare X | XCl2And (3) a solid-phase composite electrode.
Further, X powder and XCl2And after the powder is uniformly mixed, adding an additive, and then sintering in a gas protection atmosphere, wherein the additive is Al powder, FeS, S, NaI, NaBr or NaF.
Compared with the prior art, the invention has at least the following beneficial technical effects:
(1) the metal graphite battery technology provided by the invention has the advantage that the whole life cycle energy storage cost is as low as 0.04 kWh per cycle-1Far below the current mainstream energy storage battery technology.
For the battery provided by the invention, the whole life cycle single cycle energy storage cost only containing battery materials (current collectors, positive and negative active materials and electrolyte) is lower than 0.008 KWh-1According to the fact that the service life of the battery is 10000 times, the energy storage efficiency is 80%, the cost of a single battery accounts for about 25% of the total cost of the energy storage scheme, and the commercialized energy storage technology (including an energy storage module, a battery management system, inverter equipment and the like) of the metal graphite battery can be calculatedEnergy solution cost) full life cycle single cycle energy storage cost less than 0.04$-1Which is about one third of the existing lithium ion battery technology.
This is due to the negative active material metal X, XCl in this battery technology2Very low cost graphite and anode material, while YAlCl in saturated YCl4The electrolyte can be prepared from YCl and AlCl3The composite material is obtained by mixing and heating, and the composite materials of the active material and the electrolyte of the battery are very cheap and abundant, and the treatment process is simple.
(2) The metal graphite battery provided by the invention generates X and XCl at the negative electrode during charging and discharging2The solid-solid conversion process is carried out, and the dendritic crystal generation risk is avoided. YAlCl with saturated YCl as electrolyte4The metal X loses electrons during discharge to obtain excess Cl of YCl in the electrolyte-And is converted to XCl2(ii) a Due to the generated XCl2In YAlCl4Hardly dissolved in the electrolyte, and therefore, will exist as a solid phase on the surface of the negative electrode, and the negative electrode reaction is X and XCl2The solid-solid conversion process.
In addition, since all X2+Directly with Cl-Bound to form XCl in solid phase2Almost no free X is present in the electrolyte2+Therefore, there is no X in charging2+The deposition process of (3); due to the absence of X2+The deposition process of (2) puts an end to the risk that the negative electrode generates dendrites to cause short circuit of the battery, thereby greatly improving the operation stability and safety of the battery.
(3) The metal graphite battery provided by the invention has the advantages that through experimental tests, the cycle life is more than 10000 times, and the metal graphite battery can run for about 27 years by calculating the charge-discharge cycle once a day. The ultra-long cycle life is attributed to the ultra-high operating stability of the anode and cathode: during charging and discharging, X and XCl are generated at the negative electrode of the battery2The solid-solid conversion process has no dendritic crystal generation risk and very high operation stability; while the positive electrode side is charged, AlCl in the electrolyte4 -AlCl embedded between graphite positive electrode layers and embedded between graphite layers during discharge4 -The electrolyte is removed, and the reversibility of the whole process is very highStrong and extremely high operation stability.
(4) The metal graphite battery provided by the invention has excellent charge-discharge rate performance, and the charge-discharge current density can reach 10000 mA-g for a graphite cathode material-1The battery can be charged and discharged at a rate of 100C with a large rate. The excellent high-current charging and discharging power is mainly due to the fact that the molten salt electrolyte adopted by the battery has extremely high ion transmission rate, the electrochemical reaction activity of the battery is accelerated when the battery runs at high temperature, and AlCl4 -The intercalation reaction rate and reversibility in graphite electrodes are extremely high.
(5) The metal graphite battery provided by the invention has excellent technical safety, the battery material does not contain metal elementary substances of active metal elements such as lithium, sodium and the like, and safety accidents such as explosion and the like can not occur even if the battery is broken and exposed in air; in addition, the solid-solid conversion mechanism of the metal cathode without dendritic crystal growth also ensures that the battery has no short circuit risk and has higher charging and discharging operation safety.
In the preparation method, X | XCl is prepared by adopting a method of corroding X by liquid or gas2Compared with the solid powder preparation method, the solid-phase composite electrode has the advantages of simple and convenient process, low operation difficulty and lower cost.
Drawings
FIG. 1 is a schematic diagram of the discharge principle of a metal graphite battery;
FIG. 2 is a graph showing the cycle performance of the metal-graphite battery according to the present invention;
FIG. 3 is a graph of the voltage of a battery at different cycles;
FIG. 4 is an exploded view of a battery junction;
in the drawings: 1-upper cover, 2-negative pole, 3-sealing washer, 4-positive pole, 5-current collector, 6-lower cover, 12-containing washer.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Referring to fig. 4, a metal graphite medium temperature energy storage battery, includes negative pole 2, seal ring 3, anodal 4 and the current collector 5 that sets gradually from top to bottom, seal ring 3 is cylindric, the bottom is provided with anodal 4 in seal ring 3, a plurality of zonulae occludens's holding packing ring 12 has set gradually along vertical direction in anodal 4 top, there is electrolyte in holding packing ring 12, seal ring 3 upper portion is provided with the negative pole, seal ring 3 lower part is provided with the current collector, therefore seal ring 3 keeps apart positive negative pole, the emergence of battery short circuit has been avoided. The negative electrode 2, the sealing washer 3, the positive electrode 4 and the current collector 5 are all arranged in a shell, the shell comprises an upper cover 1 and a lower cover 6, the upper cover 1 is made of stainless steel materials, and the lower cover 6 is a positive electrode cap. The sealing washer 3 and the accommodating washer 12 are both made of polytetrafluoroethylene.
In the fully charged state, the negative electrode, positive electrode and electrolyte composition were as follows:
the material of the negative electrode 2 is metal X, and X is Ni, Fe, Cr, Pb, Zn or Mn;
the anode 4 is made of AlCl embedded in the anode4 -The graphite material of (2), wherein the graphite material comprises graphite, graphene, carbon nanotubes, graphite felt or carbon felt material; YAlCl with saturated YCl as electrolyte4The molten salt electrolyte solution, wherein Y is Li or Na or K or a mixture of Li, Na and K in any proportion.
Referring to fig. 1, the working principle of the metal graphite medium-temperature energy storage battery is as follows:
in the fully charged state: the negative electrode is metal X, and the positive electrode is embedded with AlCl4 -The electrolyte is YAlCl of saturated YCl4A molten salt electrolyte solution;
in the discharge state: the negative metal X loses electrons to form X2+，X2+Combined with Cl-provided by YCl to form solid phase XCl2(ii) a At this time, the negative electrode becomes X | XCl2And (3) a solid-phase composite electrode. On discharge as a whole, the negative side gives Y+Into an electrolyte; AlCl on positive side4 -The graphite is separated from the interlayer and enters the electrolyte, and the positive electrode is changed into a graphite material; one of the molten salt electrolytes with the lowest melting point is adopted, the operation temperature of the battery is 100-200 ℃, the cycle life is more than 10000 times, and the balance voltage is related to the selection of the cathode metal and is about 1-1.7V.
The negative reaction of the cell is:
the positive electrode reaction is:
the total reaction formula of the battery is as follows:
in the formula, CnShowing a multilayer graphite.
The battery is assembled in a full discharge state, and the preparation method of the positive electrode, the negative electrode and the electrolyte of the metal graphite medium-temperature energy storage battery comprises the following steps:
preparing a negative electrode: due to the embedded AlCl4 -The graphite electrode is not easily available, so the metal graphite battery is generally assembled in a full discharge state, and a layer of XCl is corroded on the surface of the metal X of the negative electrode in advance2Active substances, i.e. preparation of X | XCl2A solid phase composite electrode in which the active material is XCl2And X is a conductive current collector. For X | XCl2The invention provides a solid-phase composite electrode, and provides three preparation methods, which specifically comprise the following steps:
method one, preparing X | XCl by using HCl gas corrosion2The solid phase composite electrode comprises the following steps:
putting the cleaned and polished X electrode with known mass into a closed container filled with HCl gas, standing, controlling the temperature and the corrosion time, drying and weighing the corroded X electrode after the corrosion is finished, and comparing the mass difference of the electrode before and after the corrosion to obtain X | XCl2The mass of Cl element in the solid phase composite electrode can be used to obtain the active XCl2The quality of (c). According to the activity XCl2The mass of (a) can be calculated to obtain battery performance parameters, such as energy density, etc.
In the large-scale preparation of X | XCl2Solid phase composite electrodeIn this case, the HCl gas in the container used in the above process may be provided by a device dedicated to the production of HCl gas; when preparing X | XCl in small amount2When the electrode is compounded, a closed container containing a small amount of concentrated hydrochloric acid can be directly used, the X electrode is suspended above the closed container, and HCl gas volatilized by the concentrated hydrochloric acid is used for corrosion.
Compared with the preparation method by a solid powder method, the method has the advantages of simple and convenient process, low operation difficulty and lower cost.
Method II, preparing X | XCl by using hydrochloric acid corrosion2The solid phase composite electrode comprises the following steps:
corroding the X electrode with hydrochloric acid with known concentration to ensure that a layer of hydrochloric acid is uniformly soaked on the surface of the X electrode and reacts completely, and then drying the X electrode to ensure that no XCl exists2The dissolution loss is compared with the electrode quality difference before and after corrosion, namely X | XCl2The mass of Cl element in the solid phase composite electrode can be known, so that the activity XCl is known2And (4) quality.
Method III, using X powder and XCl2Preparation of X | XCl from powder2The solid phase composite electrode comprises the following steps:
using X powder, XCl2Ball milling the powder to refine the particles, and grinding the refined X powder and XCl2Mixing the powders, wherein X powder and XCl powder2Molar ratio of powder (2-3): 1, adding additive (Al powder, FeS, S, NaI, NaBr or NaF), sintering in gas protection atmosphere (argon or nitrogen), and making into X | XCl2And (3) a solid-phase composite electrode. The additive is completely dissolved into the electrolyte during discharging after the battery is assembled, more fine holes are generated on the negative electrode side, and the active area of the electrode can be further increased.
A positive electrode material: the positive electrode graphite material mainly comprises graphite, graphene, carbon nanotubes, graphite felt, carbon felt and other electrodes which adopt graphite as an active material.
Preparing an electrolyte: YAlCl adopting saturated YCl for metal graphite battery4Electrolytes selected from the group consisting of YCl and AlCl3Mixing completely, heating to 175 deg.C to obtain YCl and AlCl3Is greater than 1, i.e.
YCl+AlCl3→YAlCl4
YCl and AlCl3Heating the mixture at a molar ratio of 1:1 to produce YAlCl4When YCl and AlCl3When the molar ratio is more than 1, the saturated YAlCl of YCl is generated4An electrolyte.
Example 1
NaAlCl with Fe as cathode metal and NaCl as electrolyte4Molten salt electrolyte, the positive electrode being carbon cloth or carbon felt, i.e. Fe | FeCl2|NaAlCl4The (saturated NaCl) | Graphite battery is taken as an example, tests show that the battery stably circulates for more than 11000 times at the coulombic efficiency of 99.4%, the capacity after final circulation is only attenuated by 3% compared with the initial capacity, and the current density and the specific capacity in the graph are respectively 104mAh/g and 10000mA/g calculated relative to the positive electrode Graphite material. The metal iron is used as the negative electrode, so that the cost is low, and the working voltage of the obtained battery is high. The negative electrode material is prepared by the first method.
Example 2
NaAlCl with negative electrode metal as foam Ni and electrolyte as saturated NaCl4Molten salt electrolyte and carbon cloth as positive electrode are assembled into foam Ni NiCl2|NaAlCl4(saturated NaCl) | Graphite cell.
Wherein the negative electrode material is prepared by the second method, and a layer of NiCl is uniformly adhered to the surface of the foamed Ni2The assembled battery is tested, and the battery can continuously and stably work.
Example 3
NaAlCl with Zn as negative metal and NaCl as electrolyte4Molten salt electrolyte, three-dimensional graphene as anode, namely Zn | ZnCl2|NaAlCl4(saturated NaCl) | graphene batteries.
The anode material is prepared by the method III and is prepared by mixing the following raw materials in a molar ratio of 2.6: 1X powder and XCl2The powder and the additive are Al powder which are uniformly mixed and sintered into tablets. The assembled battery was tested and found to be also capable of sustained and stable operation.
Example 4
KAlCl with Cr as negative electrode metal and KCl as electrolyte4Molten salt electrolyte, positive electrode of graphite, i.e. Cr | CrCl2|KAlCl4(saturated KCl) | graphene battery.
The cathode material is prepared by the method III and is prepared by mixing the following raw materials in a molar ratio of 2: 1 Cr powder and Cr Cl2The powder and the additive FeS are uniformly mixed and sintered into tablets. The assembled battery was tested and found to be also capable of sustained and stable operation.
Example 5
NaAlCl with negative electrode metal as Pb and electrolyte as saturated NaCl4Molten salt electrolyte, and carbon nanotube as positive electrode, i.e. Pb | Pb Cl2|NaAlCl4(saturated NaCl) | graphene batteries.
The cathode material is prepared by the method III and is prepared by mixing the following raw materials in a molar ratio of 3: 1 Pb powder and Pb Cl2The powder and the additive S are uniformly mixed and sintered into tablets. The assembled battery was tested and found to be also capable of sustained and stable operation.
Example 6
NaAlCl with Mn as cathode metal and NaCl as electrolyte4Molten salt electrolyte, graphite felt as positive electrode, Mn | Mn Cl2|NaAlCl4(saturated NaCl) | graphene batteries.
The anode material is prepared by the method III and is prepared by mixing the following raw materials in a molar ratio of 2.5: 1 Mn powder and MnCl2Powder and additive NaI. Uniformly mixing and sintering into tablets. The assembled battery was tested and found to be also capable of sustained and stable operation.
Example 7
NaAlCl with Mn as cathode metal and NaCl as electrolyte4Molten salt electrolyte, graphite felt as positive electrode, Mn | Mn Cl2|NaAlCl4(saturated NaCl) | graphene batteries.
The anode material is prepared by the method III and is prepared by mixing the following raw materials in a molar ratio of 2.5: 1 Mn powder and MnCl2Powder and an additive NaBr. Uniformly mixing and sintering into tablets. The assembled battery was tested and found to be also capable of sustained and stable operation.
Example 8
NaAlCl with Mn as cathode metal and NaCl as electrolyte4Molten salt electrolyte, graphite felt as positive electrode, Mn | Mn Cl2|NaAlCl4(saturated NaCl) | graphene batteries.
The anode material is prepared by the method III and is prepared by mixing the following raw materials in a molar ratio of 2.5: 1 Mn powder and MnCl2Powder and additive NaF. Uniformly mixing and sintering into tablets. The assembled battery was tested and found to be also capable of sustained and stable operation.
In addition, the voltage curves of the cell at different cycles are shown in fig. 3. As can be seen in fig. 3, the battery capacity slightly increased in the initial period of the cycle and hardly decayed in the subsequent cycles. In addition, it can be determined from the figure that the equilibrium voltage of the battery is about 1.4V, which shows that the battery has the advantage of higher operating voltage.
The most important condition of battery technology suitable for the large-scale commercial power grid energy storage market is that the cost of the full-period single-cycle energy storage of the battery needs to be lower than the economic benefit obtained by the energy storage technology in the local power market. From the perspective of cost, compared with the existing battery technology, the battery energy storage technology adopting the molten salt electrolyte has obvious advantages: the cost of the molten salt electrolyte is far lower than that of the common non-aqueous electrolyte, such as ionic liquid and organic electrolyte; compared with a normal-temperature water system electrolyte potential window, the molten salt electrolyte has a wider potential window, so that the selectable electrode system is very abundant, and the battery voltage is not limited by the water decomposition potential in the water system electrolyte; and thirdly, because the molten salt batteries need to operate at a temperature higher than room temperature, the reaction activity of the electrode is enhanced at high temperature, and molten salt has a very high ion transmission rate, the batteries adopting the molten salt electrolyte have very excellent rate performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
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