CN109950640A - Metallic graphite carbon medium temperature energy-storage battery and preparation method thereof - Google Patents
Metallic graphite carbon medium temperature energy-storage battery and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 65
- 239000010439 graphite Substances 0.000 title claims abstract description 65
- 238000004146 energy storage Methods 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000007790 solid phase Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 239000011780 sodium chloride Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses metallic graphite carbon medium temperature energy-storage battery and preparation method thereof, metallic graphite carbon medium temperature energy-storage batteries, it is characterised in that, including anode, cathode and electrolyte, washer is provided between the anode and cathode, electrolyte is arranged in washer, wherein, just extremely graphite type material；Electrolyte is the YAlCl for being saturated YCl4, wherein Y Li, Na or K；Cathode is X | XCl2Solid phase combination electrode, wherein X is the metal that electronegativity is higher than Al.Cell operating temperature is 100 DEG C~200 DEG C, and cycle life is more than 10000 times, balanced voltage is about 1~1.7V.
Description
Technical field
The invention belongs to electrochemical energy storage cell technical fields, and in particular to metallic graphite carbon medium temperature energy-storage battery and its preparation
Method.
Background technique
After economy undergoes the extensive style rapid growth phase of extensive resource input in China, production capacity and structural adjustment is gone to become
China's economic transition at this stage is the key content of intensive development model.Wherein energy problem is in numerous economic development fields
The most key problem, main contents are to eliminate to fall behind inefficient Energy output, promote the utilization efficiency of existing Energy output,
It greatly develops the renewable energy such as wind and solar energy and constructs smart grid to solve the distribution regulation of electric energy and efficiently utilize to ask
Topic etc., all for extensive energy storage technology, more stringent requirements are proposed for these.This is because in the power system, with energy storage skill
Art can effectively realize user demand side pipe reason, reduce peak-valley difference round the clock, smooth load, reduce power supply cost, while can be with
Promote the utilization rate of renewable energy such as wind and solar energy, improve the stability of network system operation and improves power grid electric energy matter
Amount guarantees the reliability of power supply.
Common power energy storage technology has water-storage, compressed-air energy storage, super conductive magnetic storage energy, super capacitor energy-storage, flies
Take turns energy storage and battery energy storage etc..Wherein battery energy storage is since, energy conversion efficiency low to environment and space requirement are high and cost
The advantages that relatively low, has become the first choice of extensive energy storage technology in the following smart grid.Current several mainstreams are used for
The battery technology of energy storage includes lead-acid battery, sodium-sulphur battery, all-vanadium flow battery and lithium ion battery etc..Wherein lead-acid battery
Energy density is low, and charge/discharge speed is slow, and cycle life is short, and causes serious pollution to the environment；Sodium-sulphur battery is due to solid using beta-alumina
Body electrolyte, manufacturing cost is high and thermal stability is poor, is easy to happen rupture and leads to serious safety accident；Flow battery
Also the technical issues of being faced with the critical materials such as electrolyte, electrode pad especially amberplex and energy storage is on the high side asks
Topic；Lithium ion battery is that single energy storage cost is excessively high (about in life cycle management in the key constraints that energy storage market is applied
0.12 $ kWh-1), it is difficult to be received by business energy storage market.These all limit above-mentioned battery technology in electricity to a certain extent
Application in terms of net energy storage.So the battery technology for being suitable for being commercialized large scale electric network energy storage market of exploitation novel low-cost
It is extremely urgent.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of gold suitable for extensive battery energy storage market of low cost
Belong to graphite medium temperature energy-storage battery and preparation method thereof.
In order to achieve the above objectives, metallic graphite carbon medium temperature energy-storage battery of the present invention includes anode, cathode and electrolyte；Institute
Anode is stated to be made of graphite type material；Electrolyte is the YAlCl for being saturated YCl4, the Y is Li, Na or K；The cathode is X |
XCl2Solid phase combination electrode, the X are the metal that electronegativity is higher than Al.
Further, graphite type material includes graphite, graphene, carbon nanotube, graphite felt and carbon felt material.
Further, electrolyte setting is in accommodating washer.
It further, further include for accommodating anode, cathode, electrolyte and the shell of washer.
A kind of preparation method of metallic graphite carbon medium temperature energy-storage battery, comprising the following steps:
Step 1 prepares cathode: preparation X | and XCl2 solid phase combination electrode, the X are the metal that electronegativity is higher than Al；Preparation
Electrolyte: by YCl and AlCl3Electrolyte is made after mixing.
Electrolyte is mounted in accommodating washer by step 2, places anode and cathode respectively in accommodating washer upper and lower ends,
Collector is placed in positive side, the just extremely graphite type material；
Step 3 encapsulates product made from step 2 in the shell.
Further, in step 1, X | the preparation method of XCl2 solid phase combination electrode has following three kinds:
1) metal X is put into the container full of HCl gas, the X electrode being corroded is dried and claimed after etching
Amount, comparison corrosion front and back electrode quality difference is X | XCl2Cl element quality in solid phase combination electrode, it follows that active XCl2's
Quality.
2) X electrode is corroded using the hydrochloric acid of known concentration, makes one layer of hydrochloric acid of X electrode surface homogeneous immersion, and complete
Full response dries X electrode later；The electrode quality of comparison corrosion front and back is poor, as X | XCl2Cl element in solid phase combination electrode
Quality, it can thus be appreciated that activity XCl2Quality.
3) by X powder and XCl2Powder is uniformly mixed, wherein X powder and XCl2The molar ratio of powder is (2-3): 1, in gas
It is sintered under body protection atmosphere, X is made | XCl2Solid phase combination electrode.
Further, X powder and XCl2Powder after mixing, adds additive, then under gas shield atmosphere
Sintering, the additive are Al powder, FeS, S, NaI, NaBr or NaF.
Compared with prior art, the present invention at least has technical effect beneficial below:
(1) the life cycle management energy storage cost of metallic graphite carbon battery technology provided by the invention recycles 0.04 down to every
kWh-1, far below the energy-storage battery technology of current mainstream.
For battery provided by the invention, only comprising battery material (collector, positive and negative anodes active material and electrolyte)
Life cycle management single cycle energy storage cost is lower than 0.008 kWh-1, it is 10000 times according to cell operating lifetime, energy storage efficiency
It is 80%, the commercialized storage of metallic graphite carbon battery can be then calculated in monocell cost Zhan total energy storage scheme cost about 25%
Energy technology (including energy storage mould group, the full set energy storage scheme such as battery management system and contravariant equipment cost) life cycle management single follows
Ring energy storage cost is lower than 0.04 kWh-1, the one third of about existing lithium ion battery technology.
This is because negative electrode active material metal X, XCl in this battery technology2It is extremely low with the cost of positive electrode graphite, and
It is saturated the YAlCl of YCl4Electrolyte can be by YCl and AlCl3It is obtained after being heated after mixing, the active material of battery and electrolyte
Synthesis material is extremely cheap and rich reserves, and treatment process is simple.
(2) metallic graphite carbon battery provided by the invention, X and XCl occurs for cathode when charge and discharge2Between it is solid transformed
Journey, no dendrite generate risk.Electrolyte is the YAlCl for being saturated YCl4, metal X loses electronics when electric discharge, obtains mistake in electrolyte
Measure the Cl of YCl-, and it is converted into XCl2；And due to the XCl of generation2In YAlCl4It is not almost dissolved in electrolyte, so will be negative
Pole surface exists with solid phase, therefore negative reaction is X and XCl2Between solid and solid conversion process.
In addition, due to all X2+Directly and Cl-In conjunction with the XCl for generating solid phase2, there's almost no in the electrolyte free
X2+, therefore also just there is no X when charging2+Deposition process；Since there is no X2+Deposition process, that is, prevented cathode production
Raw dendrite leads to the risk of battery short circuit, thus greatly improves operation stability and the safety of battery.
(3) metallic graphite carbon battery provided by the invention is tested by experiment, and cycle life is more than 10000 times, with daily one
Secondary charge and discharge cycles calculate, and can about run 27 years.The cycle life of overlength is attributed to the fact that the operation stability of positive and negative anodes superelevation: filling
When electric discharge, X and XCl occurs for battery cathode2Conversion process admittedly, no dendrite generates risk, has very high stable
Property；And AlCl of the side of the positive electrode in charging, in electrolyte4 -It is embedded in graphite anode interlayer, when electric discharge has been inserted into graphite layers
AlCl4 -Abjection enters in electrolyte, and whole process invertibity is very strong, and operation stability is high.
(4) metallic graphite carbon battery technology charge-discharge magnification performance provided by the invention is fabulous, for graphite positive electrode
Speech, charging and discharging currents density is up to 10000mAg-1, battery can be with the rate of 100C progress high rate charge-discharge.It is so excellent
Elegant high current charge-discharge ability mainly since the molten salt electrolyte that battery uses has high ion transportation, and
Battery runs the quickening of electrochemical reaction activity and AlCl at high temperature4 -Insertion reaction rate and invertibity in graphite electrode
It is high.
(5) metallic graphite carbon battery technology safety provided by the invention is fabulous, without lithium, sodium isoreactivity gold in battery material
The safety accidents such as explosion will not occur in cell fracture exposure air for the metal simple-substance for belonging to element；In addition metal negative electrode
No dendritic growth is shifted to new management mechanisms admittedly but also battery does not have short-circuit risks admittedly, and charge and discharge safety in operation is higher.
In preparation method, X is prepared using the method for liquid or gas attack X | XCl2Solid phase combination electrode compares solid powder
Last method preparation is compared, and process is easy, and operation difficulty is low, and cost is lower.
Detailed description of the invention
Fig. 1 is metallic graphite carbon battery discharge schematic illustration；
Fig. 2 is metallic graphite carbon cycle performance of battery test chart of the invention；
Fig. 3 is voltage curve of the battery in different circulations；
Fig. 4 is battery knot explosive view；
In attached drawing: 1- upper cover, 2- cathode, 3- seal washer, 4- anode, 5- collector, 6- lower cover, 12- accommodate washer.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
Referring to Fig. 4, a kind of metallic graphite carbon medium temperature energy-storage battery, including cathode 2, the seal washer set gradually from top to bottom
3, anode 4 and collector 5, seal washer 3 are cylindrical shape, and bottom is provided with anode 4 in seal washer 3, and 4 top of anode is along vertical
Direction is disposed with several close-connected accommodating washers 12, and accommodating inside washer 12 has electrolyte, and 3 top of seal washer is set
It is equipped with cathode, 3 lower part of seal washer is provided with collector, therefore seal washer 3 keeps apart positive and negative anodes, and it is short to avoid battery
The generation on road.Cathode 2, seal washer 3, anode 4 and collector 5, are respectively provided in the shell, and shell includes upper cover 1 and lower cover 6,
Upper cover 1 is made of stainless steel material, and lower cover 6 is positive electrode cap.Seal washer 3 and accommodating washer 12 are all made of polytetrafluoroethylene (PTFE) system
At.
Under full-charge state, cathode, anode and electrolyte composition are as follows:
The material of cathode 2 is metal X, X Ni, Fe, Cr, Pb, Zn or Mn that electronegativity is higher than Al；
The material of anode 4 is positive extremely embedded with AlCl4 -Graphite type material, graphite type material includes graphite, graphene, carbon
Nanotube, graphite felt and carbon felt material；Electrolyte is the YAlCl for being saturated YCl4Molten salt electrolyte solution, wherein Y Li, Na or
The mixture of tri- kinds of K and Li, Na or K material arbitrary proportions.
Referring to Fig.1, the working principle of metallic graphite carbon medium temperature energy-storage battery is as follows:
Under full-charge state: cathode is metal X, is just extremely embedded with AlCl4 -Graphite type material, electrolyte be saturation
The YAlCl of YCl4Molten salt electrolyte solution；
In the discharged condition: negative metal X loses electronics, forms X2+, X2+The Cl provided with YCl-In conjunction with generation solid phase
XCl2；At this point, cathode becomes X | XCl2Solid phase combination electrode.When discharging on the whole, negative side provides Y+Into electrolyte；Anode
Side AlCl4 -Deviate from from the interlayer of graphite, into electrolyte, anode becomes graphite type material；Using the fused salt that fusing point is minimum
One of electrolyte, cell operating temperature are 100 DEG C~200 DEG C, and cycle life is more than 10000 times, balanced voltage and negative metal
Selection it is related, about 1~1.7V.
The negative reaction of battery are as follows:
Anode reaction are as follows:
Battery net reaction are as follows:
In formula, CnIndicate Multi-layer graphite.
Battery assembles under full discharge condition, the positive and negative electrode of metallic graphite carbon medium temperature energy-storage battery and electrolyte preparation side
Method is as follows:
Cathode preparation: due to having been inserted into AlCl4 -Graphite electrode be not easy to obtain, therefore metallic graphite carbon battery is generally being put entirely
It is assembled under electricity condition, thus one layer of XCl out is corroded on the surface negative metal X in advance2Active material produces X | XCl2Solid phase is multiple
Composite electrode, active material is XCl in this combination electrode2, X is conductive current collector.For X | XCl2Solid phase combination electrode, this hair
Three kinds of preparation methods of bright offer, specific as follows:
Method one prepares X using HCl gas attack | XCl2Steps are as follows for solid phase combination electrode:
The X electrode of known quality after the completion of cleaning and polishing is put into the closed container full of HCl gas, is then allowed to stand
And temperature and etching time are controlled, and the X electrode being corroded is dried and weighed after etching, comparison corrosion front and back electrode matter
Amount difference is X | XCl2Cl element quality in solid phase combination electrode, it can thus be concluded that going out activity XCl2Quality.According to active XCl2's
Battery performance parameter, such as energy density can be calculated in quality.
In largely preparation X | XCl2When solid phase combination electrode, the HCl gas in container used in the above process can be by specially producing
The equipment of raw HCl gas provides；As a small amount of preparation X | XCl2When combination electrode, it can be used directly and fill the closed of a small amount of concentrated hydrochloric acid
Container, X electrode is suspended from above closed container, and the HCl gas volatilized using concentrated hydrochloric acid is corroded.
It is compared compared to solid powder method preparation, process is easy, and operation difficulty is low, and cost is lower.
Method two prepares X using hcl corrosion | XCl2Steps are as follows for solid phase combination electrode:
X electrode is corroded using the hydrochloric acid of known concentration, it is ensured that one layer of hydrochloric acid of X electrode surface homogeneous immersion, and it is complete
Full response dries X electrode later, it is ensured that without XCl2The electrode quality of dissolution loss, comparison corrosion front and back is poor, as X | XCl2Gu
Cl element quality in phase combination electrode, it can thus be appreciated that activity XCl2Quality.
Method three uses X powder and XCl2Powder prepares X | XCl2Steps are as follows for solid phase combination electrode:
Use X powder, XCl2Powder carries out particle refinement by ball milling, by the X powder and XCl after refinement2Powder mixing is equal
It is even, wherein X powder and XCl2The molar ratio (2-3) of powder: 1, then be added additive (additive be Al powder, FeS, S, NaI,
NaBr or NaF), (argon gas or nitrogen) is sintered under gas shield atmosphere, X is made | XCl2Solid phase combination electrode.Wherein additive
After battery assembly, when electric discharge, is fully immersed into electrolyte, is generated more subtle holes in negative side, can be further increased electricity
Pole active area.
Positive electrode: positive graphite type material mainly includes the institutes such as graphite, graphene, carbon nanotube, graphite felt and carbon felt
Have using electrode of the graphite as active material.
Electrolyte preparation: metallic graphite carbon battery is using the YAlCl for being saturated YCl4Electrolyte, can be by YCl and AlCl3It is sufficiently mixed
It is heated to 175 DEG C after conjunction to be made, YCl and AlCl3Molar ratio be greater than 1, i.e.,
YCl+AlCl3→YAlCl4
YCl and AlCl3When molar ratio is 1:1, the two heating is generated into YAlCl4, as YCl and AlCl3Molar ratio
The YAlCl of YCl saturation is generated when greater than 14Electrolyte.
Embodiment 1
It is Fe with negative metal, electrolyte is the NaAlCl for being saturated NaCl4Molten salt electrolyte, just extremely carbon cloth or carbon
Felt, i.e. Fe | FeCl2|NaAlCl4(saturation NaCl) | for Graphite battery, after tested, battery is with 99.4% coulombic efficiency
Stabilization circulates beyond 11000 times, and the capacity after finally recycling only has decayed 3% compared with initial capacity, and electric current is close in figure
Degree and specific capacity are calculated both with respect to positive graphite material, respectively 104mAh/g and 10000mA/g.Use metallic iron as negative
Pole, the operating voltage of battery that is at low cost, obtaining are high.Wherein negative electrode material is made using the above method one.
Embodiment 2
Using negative metal as foam Ni, electrolyte is the NaAlCl for being saturated NaCl4Molten salt electrolyte, just extremely carbon cloth, group
Dress up foam Ni | NiCl2|NaAlCl4(saturation NaCl) | Graphite battery.
Wherein negative electrode material is made using the above method two, and foam Ni uniformly adheres to layer of Ni Cl in surface2To assembling
Battery tested, discovery battery can be continual and steady work.
Embodiment 3
It is Zn with negative metal, electrolyte is the NaAlCl for being saturated NaCl4Molten salt electrolyte, just extremely three-dimensional grapheme,
That is Zn | ZnCl2|NaAlCl4(saturation NaCl) | graphene battery.
Wherein, negative electrode material is made using the above method three, the X powder and XCl for being 2.6:1 with molar ratio2Powder and add
Adding agent is that Al powder is uniformly mixed and is sintered in flakes.Assembled battery is tested, discovery battery equally can be continual and steady
Work.
Embodiment 4
It is Cr with negative metal, electrolyte is the KAlCl for being saturated KCl4Molten salt electrolyte, just extremely graphite, i.e. Cr | CrCl2
|KAlCl4(saturation KCl) | graphene battery.
Wherein, negative electrode material is made using the above method three, the Cr powder and Cr Cl for being 2:1 with molar ratio2Powder and add
Add agent FeS uniformly to mix and is sintered in flakes.Assembled battery is tested, the work that discovery battery equally can be continual and steady
Make.
Embodiment 5
It is Pb with negative metal, electrolyte is the NaAlCl for being saturated NaCl4Molten salt electrolyte, just extremely carbon nanotube, i.e.,
Pb|Pb Cl2|NaAlCl4(saturation NaCl) | graphene battery.
Wherein, negative electrode material is made using the above method three, the Pb powder and Pb Cl for being 3:1 with molar ratio2Powder and add
Add agent S uniformly to mix and is sintered in flakes.Assembled battery is tested, the work that discovery battery equally can be continual and steady
Make.
Embodiment 6
It is Mn with negative metal, electrolyte is the NaAlCl for being saturated NaCl4Molten salt electrolyte, just extremely graphite felt, i.e. Mn |
Mn Cl2|NaAlCl4(saturation NaCl) | graphene battery.
Wherein, negative electrode material is made using the above method three, the Mn powder and MnCl for being 2.5:1 with molar ratio2Powder and
Additive NaI.It uniformly mixes and is sintered in flakes.Assembled battery is tested, discovery battery equally can be continual and steady
Work.
Embodiment 7
It is Mn with negative metal, electrolyte is the NaAlCl for being saturated NaCl4Molten salt electrolyte, just extremely graphite felt, i.e. Mn |
Mn Cl2|NaAlCl4(saturation NaCl) | graphene battery.
Wherein, negative electrode material is made using the above method three, the Mn powder and MnCl for being 2.5:1 with molar ratio2Powder and
Additive NaBr.It uniformly mixes and is sintered in flakes.Assembled battery is tested, discovery battery equally can be continual and steady
Work.
Embodiment 8
It is Mn with negative metal, electrolyte is the NaAlCl for being saturated NaCl4Molten salt electrolyte, just extremely graphite felt, i.e. Mn |
Mn Cl2|NaAlCl4(saturation NaCl) | graphene battery.
Wherein, negative electrode material is made using the above method three, the Mn powder and MnCl for being 2.5:1 with molar ratio2Powder and
Additive NaF.It uniformly mixes and is sintered in flakes.Assembled battery is tested, discovery battery equally can be continual and steady
Work.
In addition, voltage curve of the battery in different circulations is shown in Fig. 3.As can be seen that circulation initial cell capacity omits in Fig. 3
There is rising, and almost without decaying in subsequent circulation.In addition, can also determine that the balanced voltage of battery is about from figure
1.4V illustrates that the battery has the advantages that operating voltage is higher.
The most important condition of battery technology suitable for being commercialized large scale electric network energy storage market is that the complete period of battery is single
Secondary circulation energy storage cost is needed lower than the economic well-being of workers and staff obtained using energy storage technology in local electricity market.Go out from the angle of cost
Hair, compares existing battery technology, it can be found that the battery energy storage technology using molten salt electrolyte has apparent advantage: 1. melting
The cost of salt electrolyte is far below common non-water system electrolyte, such as ionic liquid and organic electrolyte；2. molten salt electrolyte phase
Broader than in room temperature water system electrolyte potential window, so that optional electrode system is very rich, cell voltage not will receive
The limitation of water decomposition current potential in water system electrolyte；3. since molten salt battery requires to run at temperatures greater than room temperature, in height
The reactivity of the lower electrode of temperature is enhanced, and molten state fused salt also has high ion transportation, so using fused salt electricity
The battery of solution matter can possess very outstanding high rate performance.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press
According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention
Protection scope within.
Claims (9)
1. metallic graphite carbon medium temperature energy-storage battery, which is characterized in that including positive (4), cathode (2) and electrolyte；The anode (4)
It is made of graphite type material；Electrolyte is the YAlCl for being saturated YCl4, the Y is Li, Na or K；The cathode (2) is X | XCl2Gu
Phase combination electrode, the X are the metal that electronegativity is higher than Al.
2. metallic graphite carbon medium temperature energy-storage battery according to claim 1, which is characterized in that graphite type material include graphite,
Graphene, carbon nanotube, graphite felt and carbon felt material.
3. metallic graphite carbon medium temperature energy-storage battery according to claim 1, which is characterized in that the anode (4) and cathode (2)
Between be provided with accommodating washer (12), electrolyte setting accommodating washer (12) in.
4. metallic graphite carbon medium temperature energy-storage battery according to claim 1, which is characterized in that further include for accommodating anode
(4), the shell of cathode (2), electrolyte and accommodating washer (12).
5. a kind of preparation method of metallic graphite carbon medium temperature energy-storage battery, which comprises the following steps:
Step 1 prepares cathode (2): preparing one layer of X on the surface metal X | XCl2Solid phase combination electrode, the X are higher than for electronegativity
The metal of Al；Prepare electrolyte: by YCl and AlCl3Electrolyte is made after mixing；
Electrolyte is mounted in accommodating washer (12) by step 2, is placed respectively in accommodating washer (12) upper and lower ends positive and negative
Collector is placed in positive (4) side in pole, and the anode (4) is made of graphite type material；
Step 3 encapsulates product made from step 2 in the shell.
6. the preparation method of metallic graphite carbon medium temperature energy-storage battery according to claim 5, which is characterized in that in step 1,
The surface metal X prepares one layer of X | XCl2The method of solid phase combination electrode are as follows:
Metal X is put into the container full of HCl gas, the X electrode being corroded is dried and weighed after etching, is compared
Corrosion front and back electrode quality difference is X | XCl2Cl element quality in solid phase combination electrode, it follows that active XCl2Quality.
7. the preparation method of metallic graphite carbon medium temperature energy-storage battery according to claim 5, which is characterized in that in step 1,
The surface metal X prepares one layer of X | XCl2The method of solid phase combination electrode are as follows: X electrode is carried out using the hydrochloric acid of known concentration rotten
Erosion, makes one layer of hydrochloric acid of X electrode surface homogeneous immersion, and react completely, dries X electrode later；The electrode matter of comparison corrosion front and back
Measure poor, as X | XCl2Cl element quality in solid phase combination electrode, it can thus be appreciated that activity XCl2Quality.
8. the preparation method of metallic graphite carbon medium temperature energy-storage battery according to claim 5, which is characterized in that in step 1,
The surface metal X prepares one layer of X | XCl2The method of solid phase combination electrode are as follows: by X powder and XCl2Powder is uniformly mixed, wherein X powder
End and XCl2The molar ratio of powder is (2-3): 1, be sintered under gas shield atmosphere, X is made | XCl2Solid phase combination electrode.
9. the preparation method of metallic graphite carbon medium temperature energy-storage battery according to claim 8, which is characterized in that X powder and XCl2
Powder after mixing, adds additive, is then sintered under gas shield atmosphere, the additive be Al powder, FeS, S,
NaI, NaBr or NaF.
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| CN110890539A (en) * | 2019-11-18 | 2020-03-17 | 西安交通大学 | Soft-package metal graphite medium-temperature energy storage battery and preparation method thereof |
| CN113972372A (en) * | 2021-09-26 | 2022-01-25 | 西安交通大学 | Metal graphite medium-temperature energy storage battery and preparation method thereof |
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Effective date of registration: 20231208 Address after: Room 035, F2003, 20th Floor, Building 4-A, Xixian Financial Port, Fengdong New City Energy Jinmao District, Xixian New District, Xi'an City, Shaanxi Province, 710086 Patentee after: Ningshi Special Energy Storage Technology Co.,Ltd. in Xixian New Area Address before: 710049 No. 28 West Xianning Road, Shaanxi, Xi'an Patentee before: XI'AN JIAOTONG University |