CN106688133A - Electrolyte additives for transition metal cyanometallate electrode stabilization - Google Patents
Electrolyte additives for transition metal cyanometallate electrode stabilization Download PDFInfo
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- CN106688133A CN106688133A CN201580035681.8A CN201580035681A CN106688133A CN 106688133 A CN106688133 A CN 106688133A CN 201580035681 A CN201580035681 A CN 201580035681A CN 106688133 A CN106688133 A CN 106688133A
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A method is provided for the self-repair of a transition metal cyanometallate (TMCM) battery electrode. The battery is made from a TMCM cathode, an anode, and an electrolyte including solution formed from a solvent and an alkali or alkaline earth salt. The electrolyte includes an additive represented as G-R-g: where G and g are independently include materials with nitrogen (N) sulfur (S), oxygen (O), or combinations of the above-recited elements; and where R is an alkene or alkane group. In response to charging and discharging the battery in a plurality of cycles, the method creates vacancies in a surface of the TMCM cathode. Then, the method fills the vacancies in the surface of the TMCM cathode with the electrolyte additive. An electrolyte and TMCM battery using the above-mentioned additives are also provided.
Description
Technical field
This patent disclosure relates generally to electrochemical cell, is used to make transition metal cyanogen close metal acid-salt more particularly, to containing
The electrolyte of the stable additive of battery.
Background technology
To as rechargeable lithium ion battery [patent document 1, patent document 2], sodium-ion battery [patent document
3, patent document 4] and kalium ion battery [patent document 5] cathode material, with big gap transition metal cyanogen alloy
Category hydrochlorate (TMCM) is studied.In the case of the aqueous electrolyte containing appropriate alkali metal ion or ammonium ion, six
Cyanogen closes ferrous acid cupro-nickel ((Cu, Ni)-HCF) and shows good cycle life, 40000 circulations under the charging and discharging currents of 17C
83% capacity [patent document 6- patent documents 8] is maintained afterwards.However, the material in the aqueous electrolyte is because following original
Thus show low capacity and energy density：(1) each Cu-HCF or Ni-HCF formula can be only inserted into/extract a sodium from
Son, and (2) are due to aqueous electrochemical window, these transition metal cyanogen close ferrite (TM-HCF) electrode must be under less than 1.23V
Work.The electrochemical window of material is the voltage range that material is neither aoxidized nor reduced.The scope is weight to the efficiency of electrode
Want, once super go beyond the scope, water is just changed into being electrolysed, predation is intended for use the electric energy of other electrochemical reactions.
In order to overcome the shortcoming, Hexacyanoferrate manganese (Mn-HCF) and Hexacyanoferrate iron (Fe-HCF) are used as into non-water power
The cathode material [patent document 9, patent document 10] of Xie Zhizhong.Assemble together with sodium metal anode, Mn-HCF and Fe-HCF is electric
Pole is circulated and provides the capacity of about 110 per gram of MAHs (mAh/g) between 2.0V and 4.2V.
It should be noted that the actual capacity of TMHCF electrodes is much smaller than theoretical value.For example, the theoretical capacity of Mn-HCF is
170mAh/g, but when testing in sodium-ion battery, the capacity reported only has～120mAh/g.The capacity difference is attributable to
The structure and composition of TMHCF.Buser etc. [patent document 11] have studied Prussian blue (PB)-Fe4[Fe(CN)6]3·xH2O's
Crystal structure, and find Fe (CN)6Position is only partially occupied.Room cause water enter PB gaps and or even with lattice in Fe
(III) [patent document 12] is associated.In view of charging neutrality and gap, the gap for reducing TMHCF is all played in both room and water
In mobile ion (mobile ion) concentration effect.For example, the reason for Matsuda etc. [patent document 9] is because of room
And more first-selected use A4x-2MA[MB(CN)6]x·zH2O substitutes name formula (nominal formula) A2MAMB(CN)6.Additionally, empty
Position causes intensive defect on the surface of TMHCF.Without interstitial ion and Zhi Chishui (supporting water), surface holds
Easily cave in.When being extracted away during electrochemical reaction in the interstitial ion of near surface, surface deterioration can be increased.
In battery, such deterioration causes capability retention poor.
In Li+In the case of-ionic electrolytes, Cu-HCF electrodes provide the appearance of 120mAh/g during first time discharges
Amount, but its capacity is down to 40mAh/g [patent document 13] in 10 circulations.By being coated with Ni-HCF, Cu-HCF electrodes
Surface be modified and improve its stability.However, (undercoordinated) of infull coordination on a surface
Transition metal (UTM) hinders the electric charge between TMHCF electrodes and electrolyte due to the charge repulsion between UTM and mobile ion
Transmission, this may cause high rate performance poor.Park etc. [patent document 14] is mentioned in the Fe with the infull coordination at surface2 +/Fe3+LiFePO4Skin effect on electrode generates Li+Across the barrier of electrolyte/electrode interface transmission.In order to improve appearance
Amount conservation rate, some researchers optimize the synthesis of TMHCF with the defect on the surface for reducing them and in body of material and
Room [patent document 15, patent document 16].These zero defects TMHCF shows longer cycle life.
Prior art literature
Non-patent literature
Patent document 1：V.D.Neff, some performance characteristics (Some performance of Prussian blue battery
Characteristics of a Prussian Blue battery), ECS's magazine (Journal of
Electrochemical Society), 132 (1985) 1382-1384.
Patent document 2：N.Imanishi, T.Morikawa, J.Kondo, Y.Takeda, O.Yamamoto,
N.Kinugasa, T.Yamagishi, are embedded in as the embedding lithium behavior in the iron cyanide complex compound of the positive pole of lithium secondary battery
(Lithium Intercalation Behavior into Iron Cyanide Complex as Positive
Electrode of Lithium Secondary Battery), power supply magazine (Journal of Power Sources), 79
(1999)215-219。
Patent document 3：Y.Lu, L.Wang, J.Cheng, J.B.Goodenough, it is Prussian blue：The new frame of sode cell
(Prussian blue：A new framework for sodium batteries), chemical communication (Chemistry
Communications), 48 (2012) 6544-6546.
Patent document 4：L.Wang, Y.Lu, J.Liu, M.Xu, J.Cheng, D.Zhang, J.B.Goodenough, are used for
The excellent inexpensive negative electrode (A superior low-cost cathode for a Na-ion battery) of sodium-ion battery,
Applied chemistry world version (Angewandte Chemie International Edition), 52 (2013) 1964-1967.
Patent document 5：A.Eftekhari, the potassium secondary cell (Potassium based on Prussian blue negative electrode
Secondary cell based on Prussian blue cathode), power supply magazine (Journal of Power
Sources), 126 (2004) 221-228.
Patent document 6：C.D.Wessells, R.A.Huggins, Y.Cui, with long circulation life and high-power six cyanogen
Close coppe ferrite battery electrode (Copper hexa cyanoferrate battery electrodes with long cycle
Life and high power), naturally (Nature Communications) is communicated, 2 (2011) 550.
Patent document 7：C.D.Wessells, S.V.Peddada, R.A.Huggins, Y.Cui, for aqueous sodium and potassium
Hexacyanoferrate nickel nano particle electrode (the Nickel hexacyanoferrate nanoparticle of ion battery
Electrodes for aqueous sodium and potassium ion batteries). nanometer bulletin (Nano
Letters), 11 (2011) 5421-5425.
Patent document 8：C.D.Wessells, S.V.Peddada, M.T.McDowell, R.A.Huggins, Y.Cui, insert
Enter impact (The effect of insertion of the species to nanostructured open frame hexacyanoferrate battery electrode
species on nano structured open framework hexacyanoferrate battery
Electrode), ECS's magazine (Journal of the Electrochemical Society), 159 (2012)
A98-A103。
Patent document 9：T.Matsuda, M.Takachi, Y.Moritomo, for the sodium manganese ferrocyanide of Na ion batteries
Thing film (A sodium manganese ferrocyanide thin film for Na-ion batteries), chemistry is logical
News (Chemical Communications), DOI：10.1039/C3CC38839E.
Patent document 10：S.-H.Yu, M.Shokouhimehr, T.Hyeon, Y.-E.Sung, as can for lithium and sodium
Hexacyanoferrate Fe nanometer particles (the Iron hexacyanoferrate nanoparticles of the cathode material of rechargeable battery
As cathode materials for lithium and sodium rechargeable batteries), ECS electrochemistry
Bulletin (ECS Electrochemistry Letters), 2 (2013) A39-A41.
Patent document 11：H.J.Buser, D.Schwarzenbach, W.Petter, A.Ludi, it is Prussian blue：Fe4[Fe
(CN) 6] crystal structure (the crystal structure of Prussian blue of 3xH2O：Fe4[Fe(CN)6]
3.xH2O), inorganic chemistry, 16 (1977) 2704-2710.
Patent document 12：F.Herren, P.Fischer, A.Ludi, W.Halg, Prussian blue-Fe4 [Fe (CN) 6]
The neutron-diffraction study of 3.xH2O, the position of hydrone and long-range magnetic order (Neutron diffraction study of
Prussian blue, Fe4 [Fe (CN) 6] 3.xH2O.Location of water molecules and long-range
Magnetic order), inorganic chemistry, 1980,19,956-959.
Patent document 13：D.Asakura, C, H.Li, Y.Mizuno, M.Okubo, H.Zhou, D.R.Talham, as lithium
The coordination polymer of the bimetallic cyano-bridged of ion cathode material：The core@core/shell nanoparticles that cycle performance is improved
(Bimetallic cyanide-bridged coordination polymers as lithium ion cathode
materials：Core@shell nanoparticles with enhanced Cyclability), JACS,
135(2013)2793-2799。
Patent document 14：K.-S.Park, P.Xiao, S.-Y.Kim, A.Dylla, Y.-M.Choi, G.Henkelman,
K.J.Stevenson, J.B.Goodenough, are moved by the anionic surface modifying charge transfer being improved of LiFePO4
Mechanics (Enhanced charge-transfer kinetics by anion surface modification of
LiFePO4), materials chemistry (Chem.Mater.), 24 (2012) 3212-3218.
Patent document 15：X.Wu, W.Den, J.Qian, Y.Cao, X.Ai, H.Yang, the nano-particles of monocrystalline FeFe (CN) 6：
High power capacity and high-rate cathode (Single-crystal FeFe (CN) 6nanoparticles of Na ion batteries:a high
Capacity and high rate cathode for Na-ion batteries), materials chemistry periodical A
(J.Mater.Chem.A.), 1 (2013) 10130-10134.
Patent document 16：Y.You, X.-L.Wu, Y.-X.Yin, Y.-G.Guo, as excellent the moon of room temperature sodium-ion battery
The Prussian blue crystal of high-quality (the High-quality Prussian blue crystals as superior of pole material
Cathode materials for room-temperature sodium-ion batteries), energy and environment science
(Energy＆Environmental Science), Doi：10.1039/C3EE44004D.
The content of the invention
Technical problem
However, the defect and room in TMCM electrodes is likely to the appearance during the charge and discharge cycles of battery, and they
Can not possibly be prevented by synthesizing.
Transition metal cyanogen in metal ion battery closes metal acid-salt (TMCM) electrode and has shown that by such as high-energy
Good performance indicated by density, high power density and low cost.However, the defect and room that produce in TMCM electrodes cause
Structure deterioration, which has limited their cycle life.
Solve the technical scheme of technical problem
There is disclosed herein additive agent electrolyte, the additive agent electrolyte can be with these defects and the gold around room
Category ionic interaction and coordination, so as to support the structure of TMCM, it is ensured that longer cycle life.
Correspondingly, there is provided for the method for selfreparing TMCM battery electrodes.The battery by TMCM negative electrodes, anode and
Electrolyte comprising the solution being made up of solvent and alkali metal salt or alkali salt is made.The electrolyte is also included and is expressed as
The additive of G-R-g：
Materials of the wherein G and g independently selected from the combination comprising nitrogen (N), sulphur (S) and oxygen (O) element or above-mentioned element；And
And,
Wherein R is alkene or alkane group.
In response to carrying out to battery discharge and recharge in several cycles, methods described is generated in the surface of the TMCM negative electrodes
Room.Then, the methods described additive agent electrolyte fills the room in the surface of the TMCM negative electrodes.
The solvent can for water, carbonates, furans,Alkane (oxane), ether, ketone, ester, acid amides, acetic acid esters, silica
Alkane or combinations thereof.Some examples of the salt include AxCl、AxSO4、AxNO3、AxPO4、AxBr、AxI、AxAlO2、AxAc (second
Hydrochlorate), AxPF6、AxBF6、AxClO4、AxAsF6、AxAlCl4、AxB5Cl5、AxCF3SO3、Ax(CF3SO2)2N and Ax(C2F5SO2)2N,
Wherein " A " is alkali metal or alkali earth metal.In one aspect, the R olefin/paraffins can with such as oxygen, silicon,
Formed in the case of the substituent (substation) of fluorine, chlorine, phosphorus, aluminium, arsenic, selenium, bromine or combinations thereof.In another side
Face, G and g are independently selected from alkene or alkane group.
The TMCM negative electrodes are by formula BnM1pM2q(CN)r·fH2O is represented；
Wherein B is alkali metal or alkaline-earth metal；
Wherein M1 and M2 are independently selected from transition metal；
Wherein n is in the range of 0 to 2；
Wherein p is less than or equal to 2；
Wherein f is in the range of 0 to 20；
Wherein q is less than or equal to 2；And
Wherein r is less than or equal to 6.
The anode can be made up of following material：Carbonaceous material, alkali metal, alkaline-earth metal, Sn-containing alloy, leaded conjunction
Gold, silicon-containing alloy, phosphorus-containing alloy, germanium-containing alloy, the titanate of alkali metal containing, the titanate of alkaline including earth metal or their group
Close.
Hereinafter provide said method, the electrolyte with additive and with battery made by above-mentioned electrolyte in addition
Details.
The beneficial effect of the invention
It is right if the additive that will be interacted with the surface of TMCM electrodes and be coordinated can be included in the electrolyte
To be favourable in eliminating and reducing the defect and the infull metal ion being coordinated and improve cycle life.
Description of the drawings
[Fig. 1] Fig. 1 is the local for closing the electrolyte of the battery of metal acid-salt (TMCM) electrode with transition metal cyanogen
Cross-sectional view.
[Fig. 2] Fig. 2 is the partial cross section view of TMCM electrode batteries.
[Fig. 3 A] Fig. 3 A depict the fresh TMCM electrodes being immersed in the electrolyte containing additive.
[Fig. 3 B] Fig. 3 B depict the defect on the surface with TMCM electrodes and interact or be coordinated and make the electrode
Constitutionally stable additive.
[Fig. 4 A] Fig. 4 A be by capacity relative to circulation in the way of show, without using the general of additive agent electrolyte
The example of Lu Shibai (PW, Na2Fe2 (CN) 6) electrode.
[Fig. 4 B] Fig. 4 B be show in the way of capacity is relative to voltage, without using the general of additive agent electrolyte
Lu Shibai (PW, Na2Fe2(CN)6) electrode example.
[Fig. 5 A] Fig. 5 A show in the way of capacity is relative to circulation, which use any additive agent electrolyte
The example of PW electrodes.
[Fig. 5 B] Fig. 5 B show in the way of capacity is relative to voltage, which use any additive agent electrolyte
The example of PW electrodes.
[Fig. 6] Fig. 6 be compare have ADN additives and without ADN additives in the case of PW electrodes figure.
[Fig. 7] Fig. 7 is the flow chart for illustrating the method for selfreparing TMCM battery electrodes.
Specific embodiment
Fig. 1 is the partial cross-section for closing the electrolyte of the battery of metal acid-salt (TMCM) electrode with transition metal cyanogen
Figure.Electrolyte 100 includes solution 102, and solution 102 includes solvent 104 and the salt that can be alkali metal salt or alkali salt.Institute
State salt reference marker 106 to represent.Also comprising the additive represented with reference marker 108, the additive bag contains electrolyte 100
G-R-g：
Wherein G and g is independently selected from the material of the combination comprising nitrogen (N), sulphur (S) and oxygen (O) element or above-mentioned element
Group.
Generally G ≠ g.However, in some cases they are identicals, such as in the case of G=g=adiponitriles.
R is alkene or alkane group.Term " independently selected from " refers to that the selected elements of G can be the selected units of g
Element can not be the selected elements of g.
Solvent 104 can for water, carbonates, furans,Alkane, ether, ketone, ester, acid amides, acetic acid esters, siloxanes or they
Combination.Some clear and definite examples of salt 106 include AxCl、AxSO4、AxNO3、AxPO4、AxBr、AxI、AxAlO2、AxAc (acetic acid
Salt), AxPF6、AxBF6、AxClO4、AxAsF6、AxAlCl4、AxB5Cl5、AxCF3SO3、Ax(CF3SO2)2N and Ax(C2F5SO2)2N, its
In " A " be alkali metal or alkali earth metal.
In one aspect, the R alkene or alkane comprising such as oxygen, silicon, fluorine, chlorine, phosphorus, aluminium, arsenic, selenium, bromine or they
The substituent (substitution) of combination.For example, if R is alkene chain-CH2-CH2-CH2-, then in some cases, R's
Some parts can be replaced and formation-CHF-CH with F2-CH2-, with O replace and formation-CH2-O-CH2- or replaced and shape with Cl
Into-CH2-CH2-CCl2-。
In one aspect, G and g is independently selected from alkene or alkane group.In other words, if G is alkene, then g can
Think alkene or alkane.Similarly, if G is alkane, then g can be alkene or alkane.As described above, G and g can not be
Identical material.However, R can be identical with G or g.Additive 108 is to the percentage by weight (weight %) of solution 102 in 0.1 weight
In the range of amount weight % of % to 50.
Fig. 2 is the partial cross section view of TMCM electrode batteries.Battery 200 includes TMCM negative electrodes 202 and anode 204.Such as
Some aspects for illustrating, ion osmosis type barrier (ion-permeable barrier) 206 can be by negative electrode 202 and anode 204
Separate.As figure 1 above explanation described in, electrolyte includes solution 102, and solution 102 includes solvent 104 and alkali metal salt or alkali
Earth metal salt 106.The electrolyte also includes additive 108, and the additive 108 includes G-R-g：
Wherein G and g is independently selected from the material of the combination comprising nitrogen (N), sulphur (S) and oxygen (O) element or above-mentioned element
Group；Also,
Wherein R is alkene or alkane group.
Solvent 104 can for water, carbonates, furans,Alkane, ether, ketone, ester, acid amides, acetic acid esters, siloxanes or they
Combination.Some clear and definite examples of salt 106 include AxCl、AxSO4、AxNO3、AxPO4、AxBr、AxI、AxAlO2、AxAc (acetic acid
Salt), AxPF6、AxBF6、AxClO4、AxAsF6、AxAlCl4、AxB5Cl5、AxCF3SO3、Ax(CF3SO2)2N and Ax(C2F5SO2)2N, its
In " A " be alkali metal or alkali earth metal.
In one aspect, the R alkene or alkane comprising such as oxygen, silicon, fluorine, chlorine, phosphorus, aluminium, arsenic, selenium, bromine or they
The substituent of combination.In yet another aspect, G and g are independently selected as alkane or alkene.As described above, G and g can not be phase
Same material, but R can be identical with G or g.Additive 108 is to the percentage by weight (weight %) of solution 102 in 0.1 weight %
To 50 weight %.
The TMCM negative electrodes 202 are by formula BnM1pM2q(CN)r·fH2O is represented；
Wherein B is first group of metal, and it can be, for example, alkali metal or alkaline-earth metal；
Wherein M1 and M2 is independently selected from second group of transition metal；
Wherein n is in the range of 0 to 2；
Wherein p is less than or equal to 2；
Wherein f is in the range of 0 to 20；
Wherein q is less than or equal to 2；And
Wherein r is less than or equal to 6.
Some examples of first group of metal comprising lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca),
Strontium (Sr), barium (Ba), silver-colored (Ag), aluminium (Al), magnesium (Mg) and combinations thereof.
M1 and M2 are each independently selected from second group of metal, and the metal includes titanium (Ti), vanadium (V), chromium (Cr), manganese
(Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), cadmium (Cd), calcium
(Ca), magnesium (Mg), strontium (Sr) and barium (Ba).M1 and M2 can be identical metal or can not be identical metal.
Anode 204 can be made up of following material：Carbonaceous material, alkali metal, alkaline-earth metal, Sn-containing alloy, lead-containing alloy,
Silicon-containing alloy, phosphorus-containing alloy, germanium-containing alloy, the titanate of alkali metal containing, the titanate of alkaline including earth metal or combinations thereof.
Fig. 3 A depict the fresh TMCM electrodes being immersed in the electrolyte containing additive.Fig. 3 B are depicted and TMCM electrodes
Surface on defect interact or be coordinated and make the constitutionally stable additive of the electrode.In the discharge and recharge of the battery
Period, mobile ion 300
Can be in TMCM electrodes 202 and to " waving " back and forth between electrode (not shown), TMCM electrodes 202 are expressed as
Especially near surface metal cyanides room or transition metal defect 302 are produced in TMCM and occur not
The metal ion 306 of full coordination so that the negative electrode is unstable.Under the electriferous state of TMCM, B ions are by completely from described
TMCM is removed, and the framework of TMCM may start to cave in due to lacking the B ions supported from the surface.Therefore, exist
In rechargeable battery with TMCM electrodes, cycle life becomes problem.In addition, because the metal ion of infull coordination and B from
Charge repulsion between son, the metal ion of infull coordination can hinder the charge transfer across interface between electrode and electrolyte.
In order that TMCM electrodes 202 are stable and reduce the defect/room 302 on its surface, using as the G- of additive 108
R-g is added in electrolyte 100.G and g represent the group containing nitrogen (N), and/or sulphur (S), and/or oxygen (O).R is to be fluorinated
Alkene or alkane group.Transition metal ions near G and g and cathode surface 304 interacts or is coordinated so that TMCM
The Stability Analysis of Structures of electrode 202.The group can also be connected to reduce it with the metal ion of the infull coordination on the surface
Repulsion to B ions.Fig. 3 B are depicted the surface of TMCM electrodes 202 is modified with the additives 108 in electrolyte 100.
Fig. 4 A and 4B be respectively by capacity relative to circulation in the way of and capacity relative to voltage in the way of show, wherein
Not using Prussia white (PW, the Na of additive agent electrolyte2Fe2(CN)6) electrode example.Containing NaClO4Carbonic acid it is sub-
In the case of the electrolyte of ethyl ester (EC)/diethyl carbonate (DEC), it is shown that in sodium metal to the PW electrodes in the case of electrode
Performance.In first circulation, PW electrodes provide the～capacity of 120mAh/g, and then capacity is decayed in 90 circulations
84mAh/g。
Fig. 5 A and 5B be respectively by capacity relative to circulation in the way of and capacity relative to voltage in the way of show, wherein
The example of the PW electrodes of any additive agent electrolyte is used.In order to improve performance, adiponitrile (ADN) be used as EC/DEC and
NaClO4Electrolyte in additive.The d- rail interactions of lone pair electrons and iron in nitrogen so that ADN chains can be filled up
Defect/room is so that PW Stability Analysis of Structures.ADN additives do not cause PW electrode charge and discharge curves (profiles) and it
The significant difference of initial capacity, but as shown as significantly improve its cycle performance.
Fig. 6 be compare have ADN additives and without ADN additives in the case of PW electrodes figure.In 90 circulations
In, the PW electrodes in the case where there is ADN additives maintain the 92.6% of its initial capacity.At identical conditions, do not having
Have in the PW electrodes in the case of ADN and only maintain the 70.1% of initial capacity.In a word, ADN makes the Stability Analysis of Structures of PW electrodes simultaneously
And improve its cycle life.
Fig. 7 is the flow chart for illustrating the method for selfreparing TMCM battery electrodes.Although for the sake of clarity according to volume
The order of number step describes the method, but numbers the order of not necessarily given step.It should be understood that some in these steps
Can skip, parallel carry out or carry out in the case where strict sequence order need not be kept.It is however generally that, the method is followed
The numerical order of the step.The method is from the beginning of step 700.
Step 702 provides the battery comprising TMCM negative electrodes, anode and electrolyte.The electrolyte is comprising solution and comprising G-
The additive of R-g, the solution includes solvent, alkali metal salt or alkali salt：
Wherein G and g is independently selected from the material of the combination comprising nitrogen (N), sulphur (S), the element of oxygen (O) or above-mentioned element
Group；Also,
Wherein R is alkene or alkane group.
As known in the art, alkene is the undersaturated aliphatic hydrocarbon with one or more carbon-to-carbon double bonds.Alkane is
The saturated hydrocarbons being only made up of with singly-bound hydrogen and carbon atom.In one aspect, additive to the percentage by weight of solution in 0.1 weight
In the range of amount weight % of % to 50.In general, the battery provided in step 702 is as above described in the explanation of Fig. 2
Battery.In response to carrying out to battery discharge and recharge in several cycles, step 704 generate in the surface of TMCM negative electrodes room and
Defect.Generally, battery is discharged by connecting external loading between the anode and the cathode.Similarly, by anode with
External power source is inserted between negative electrode so that the sense of current manifested during discharge cycles inverts and battery is charged.Step
Room and defect in 706 surfaces that TMCM negative electrodes are filled with the additive agent electrolyte.
Some examples of solvent comprising water, carbonates, furans,Alkane, ether, ketone, ester, acid amides, acetic acid esters, siloxanes and
Combinations thereof.Some examples of salt include AxCl、AxSO4、AxNO3、AxPO4、AxBr、AxI、AxAlO2、AxAc (acetate),
AxPF6、AxBF6、AxClO4、AxAsF6、AxAlCl4、AxB5Cl5、AxCF3SO3、Ax(CF3SO2)2N and Ax(C2F5SO2)2N, wherein
" A " is alkali metal or alkali earth metal.
In one aspect, the R alkene can include in following substituent：Oxygen, silicon, fluorine, chlorine, phosphorus, aluminium, arsenic,
Selenium, bromine and combinations thereof.In yet another aspect, G and g independently are alkene or alkane.It should be noted that：Listed above
Example is not the exclusive list of material.
The additive useful to the selfreparing of TMCM battery electrodes is provided to electrolyte.Have been proposed for concrete material
Example illustrating the present invention.However, the present invention is not limited only to these examples.It may occur to persons skilled in the art that of the invention
Other variants and embodiment.
All applications described below are incorporated herein by way of reference：(1) for alkali metal-ion battery
Hard carbon compound (hard carbon composite for alkali metal-ion batteries), Yuhao Lu etc. send out
Bright, sequence number on June 6th, 62/009,069,2014 submits to, attorney docket SLA3416P；(2) cyanogen alloy belongs to acid metal salt conjunction
Into method (METAL CYANOMETALLATE synthesis method), Long Wang etc. are invented, sequence number 62/008,869,
On June 6th, 2014 submits to, attorney docket SLA3430P；(3) with the chargeable metal ion of non-aqueous hybrid ionic electrolyte
Battery (RECHARGEABLE METAL-ION BATTERY WITH NON-AQUEOUS HYBRID ION ELECTROLYTE),
Long Wang etc. are invented, and sequence number on May 7th, 14/271,498,2014 submits to, attorney docket SLA3388；(4) for gold
The reactive membrane (REACTIVE SEPARATOR FOR A METAL-ION BATTERY) of category ion battery, Long Wang
Deng invention, sequence number 14/230,882, on March 31st, 2014 submits to, attorney docket SLA3370；(5) sodium superionic conductors gathers
Polymer electrolyte structure (NASICON-POLYMER ELECTROLYTE STRUCTURE), the invention such as Long Wang, sequence number
On March 6th, 14/198,755,2014 submits to, attorney docket SLA3367；(6) with having loaded the sun that can consume metal in advance
The battery (BATTERY WITH an anode preloaded with consumable metals) of pole, Yuhao Lu etc. send out
Bright, sequence number on March 6th, 14/198,702,2014 submits to, attorney docket SLA3364；(7) with the electricity of preload metal
Pond anode (BATTERY ANODE WITH PRELOADED METALS), the invention such as Long Wang, sequence number 14/198,663,
On March 6th, 2014 submits to, attorney docket SLA3363；(8) the metal battery electrode (METAL with pyrolytic coating
BATTERY ELECTRODE WITH PYROLYZED COATING), the invention such as Yuhao Lu, sequence number 14/193,782,
Submit within 2 28th, 2014, attorney docket SLA3353；(9) cyanogen of metal six with shielding construction closes metal acid-salt electrode
(METAL HEXA-CYANOMETALLATE ELECTRODE WITH SHIELD STRUCTURE), the invention such as Yuhao Lu, sequence
Row number 14/193,501,2014 year is submitted to for 28 days 2 months, attorney docket SLA3352；(10) cyanogen close metal acid-salt cathode cell and
Manufacture method (Cyanometallate Cathode Battery and Method for Fabrication), Yuhao Lu
Deng invention, sequence number 14/174,171, submit within 2 6th, 2014, attorney docket SLA3351；(11) ferrous (II)-six cyanogen
Close iron (II) acid sode cell electrode and synthetic method (SODIUM IRON (II)-HEXACYANOFERRATE (II) BATTERY
ELECTRODE AND SYNTHESIS METHOD), the invention such as Yuhao Lu, sequence number October 30 in 14/067,038,2013
Day submits to, attorney docket SLA3315；(12) cyanogen of transition metal six closes metal acid-salt conductive polymer composite
(TRANSITION Metal HexacyanoMETALLATE-CONDUCTIVE POLYMER COMPOSITE), Sean Vail
Deng invention, sequence number 14/059,599, on October 22nd, 2013 submits to, attorney docket SLA3336；(13) metal-doped mistake
Cross metal hexacyanoferrate (TMHCF) battery electrode (Metal-Doped Transition Metal Hexa-
Cyanoferrate (TMHCF) Battery Electrode), the invention such as Yuhao Lu, sequence number 13/907,892,2013 6
The moon 1 was submitted to, attorney docket SLA3287；(14) with the hexacyanoferrate battery that ferrocyanide or the iron cyanide are modified
Electrode (HEXA-CYANOFERRATE BATTERY ELECTRODE MODIFIED WITH FERRO-CYANIDES OR
FERRICYANIDES), the invention such as Yuhao Lu, sequence number on May 20th, 13/897,492,2013 submits to, attorney docket
SLA3286；(15) shielded transition metal hexacyanoferrate battery electrode (PROTECTED TRANSITION METAL
HEXACYANOFERRATE BATTERY ELECTRODE), the invention such as Yuhao Lu, sequence number in April, 13/872,673,2013
Submit within 29th, attorney docket SLA3285；(16) the transition metal hexacyanoferrate battery with single platform charging and discharging curve
Negative electrode (TRANSITION METAL HEXACYANOFERRATE BATTERY CATHODE WITH SINGLE PLATEAU
CHARGE/DISCHARGE CURVE), the invention such as Yuhao Lu, sequence number on January 29th, 13/752,930,2013 submits to, generation
Reason people's Reference Number SLA3265；(17) ultracapacitor of metal acid-salt negative electrode, active carbon anode and aqueous electrolyte is closed with six cyanogen
(SUPERCAPACITOR WITH HEXA-CYANOMETALLATE CATHODE, ACTIVATED CARBON ANODE, AND
AQUEOUS ELECTROLYTE), the invention such as Yuhao Lu, sequence number September in 13/603,322,2012 is submitted on the 4th, agent
Reference Number SLA3212；(18) six cyanogen for electrochemical applications close the improvement of the electric transmission of metal acid-salt electrode
(IMPROVEMENT OF ELECTRON TRANSPORT IN HEXACYANOMETALLATE ELECTRODE FOR
ELECTROCHEMICAL APPLICATIONS), the invention such as Yuhao Lu, sequence number on June 14th, 13/523,694,2012 carries
Hand over, attorney docket SLA3152；(19) alkali metal ion and alkaline earth of metal acid-salt negative electrode and non-metallic anode are closed with six cyanogen
Metal ion battery (ALKALI AND ALKALINE-EARTH ION BATTERIES WITH HEXACYANOMETALLATE
CATHODE AND NON-METAL ANODE), the invention such as Yuhao Lu, sequence number on April 17th, 13/449,195,2012 carries
Hand over, attorney docket SLA3151；(20) for the electrode side of being formed of the metal ion battery with six cyanogen conjunction metal acid-salt electrode
Method (Electrode Forming Process for Metal-Ion Battery with Hexacyanometallate
Electrode), the invention such as Yuhao Lu, sequence number on March 28th, 13/432,993,2012 submits to, attorney docket
SLA3146.All these applications are all incorporated herein by way of reference.
Claims (22)
1. one kind is used for the electrolyte of the battery that metal acid-salt (TMCM) electrode is closed with transition metal cyanogen, the electrolyte bag
Contain：
The solution of the salt in the group constituted comprising solvent and selected from alkali metal salt and alkali salt；
Additive comprising G-R-g：
Groups of the wherein G and g independently selected from the material of the combination comprising nitrogen (N), sulphur (S), the element of oxygen (O) and above-mentioned element；
Also,
The group that wherein R is constituted selected from alkene and alkane.
2. electrolyte according to claim 1, wherein,
The solvent selected from water, carbonates, furans,Alkane, ether, ketone, ester, acid amides, acetic acid esters, siloxanes and their group
Close the group for constituting.
3. electrolyte according to claim 1 and 2, wherein,
The group that the salt is constituted selected from following salt：AxCl、AxSO4、AxNO3、AxPO4、AxBr、AxI、AxAlO2、AxAc (acetic acid
Salt), AxPF6、AxBF6、AxClO4、AxAsF6、AxAlCl4、AxB5Cl5、AxCF3SO3、Ax(CF3SO2)2N and Ax(C2F5SO2)2N, its
In " A " selected from alkali and alkaline earth metal ions element constitute group.
4. electrolyte according to any one of claim 1 to 3, wherein,
R includes the substituent in the group constituted selected from oxygen, silicon, fluorine, chlorine, phosphorus, aluminium, arsenic, selenium, bromine and combinations thereof.
5. electrolyte according to any one of claim 1 to 4, wherein,
G and g is independently selected from the group being made up of alkane and alkene.
6. electrolyte according to any one of claim 1 to 5, wherein,
Additive is to the percentage by weight (weight %) of solution in the range of 0.1 weight % to 50 weight %.
7. a kind of transition metal cyanogen closes metal acid-salt (TMCM) electrode battery, and it is included：
TMCM negative electrodes；
Anode；
Electrolyte, it is included：
The solution of the salt in the group constituted comprising solvent and selected from alkali metal salt and alkali salt；
Additive comprising G-R-g：
Groups of the wherein G and g independently selected from the material of the combination comprising nitrogen (N), sulphur (S), the element of oxygen (O) and above-mentioned element；
Also,
The group that wherein R is constituted selected from alkene and alkane.
8. battery according to claim 7, wherein,
The solvent selected from water, carbonates, furans,Alkane, ether, ketone, ester, acid amides, acetic acid esters, siloxanes and they
The group that combination is constituted.
9. the battery according to claim 7 or 8, wherein,
The group that the salt is constituted selected from following salt：AxCl、AxSO4、AxNO3、AxPO4、AxBr、AxI、AxAlO2、AxAc (acetic acid
Salt), AxPF6、AxBF6、AxClO4、AxAsF6、AxAlCl4、AxB5Cl5、AxCF3SO3、Ax(CF3SO2)2N and Ax(C2F5SO2)2N,
The group that wherein " A " is constituted selected from alkali and alkaline earth metal ions element.
10. the battery according to any one of claim 7 to 9, wherein,
R includes the substituent in the group constituted selected from oxygen, silicon, fluorine, chlorine, phosphorus, aluminium, arsenic, selenium, bromine and combinations thereof.
11. batteries according to any one of claim 7 to 10, wherein,
G and g is independently selected from the group being made up of alkane and alkene.
12. batteries according to any one of claim 7 to 11, wherein,
Additive is to the percentage by weight (weight %) of solution in the range of 0.1 weight % to 50 weight %.
13. batteries according to any one of claim 7 to 12, wherein,
The TMCM negative electrodes are by formula BnM1pM2q(CN)r·fH2O is represented；
Wherein B is selected from first group of metal, and first group of metal is selected from the group comprising alkali and alkaline earth metal ions；
Wherein M1 and M2 is independently selected from second group of transition metal；
Wherein n is in the range of 0 to 2；
Wherein p is less than or equal to 2；
Wherein f is in the range of 0 to 20；
Wherein q is less than or equal to 2；And
Wherein r is less than or equal to 6.
14. batteries according to claim 13, wherein,
First group of metal comprising lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), strontium (Sr), barium (Ba),
Silver-colored (Ag), aluminium (Al), magnesium (Mg) and combinations thereof.
15. batteries according to claim 13 or 14, wherein,
M1 and M2 are each independently selected from second group of metal being made up of following metal：Titanium (Ti), vanadium (V), chromium (Cr), manganese
(Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), cadmium (Cd), calcium
(Ca), magnesium (Mg), strontium (Sr) and barium (Ba).
16. batteries according to any one of claim 7 to 15, wherein,
The anode is made up of the material in the group constituting selected from following material：Carbonaceous material, alkali metal, alkaline-earth metal, contain
Tin alloy, lead-containing alloy, silicon-containing alloy, phosphorus-containing alloy, germanium-containing alloy, the titanate of alkali metal containing, the metatitanic acid of alkaline including earth metal
Salt and combinations thereof.
A kind of 17. methods for closing metal acid-salt (TMCM) battery electrode for selfreparing transition metal cyanogen, methods described includes：
The battery comprising TMCM negative electrodes, anode and electrolyte is provided, the electrolyte is included：Comprising solvent, selected from alkali metal
The solution of the salt in the group that salt and alkali salt are constituted, and the additive comprising G-R-g：
Groups of the wherein G and g independently selected from the material of the combination comprising nitrogen (N), sulphur (S), the element of oxygen (O) and above-mentioned element；
The group that wherein R is constituted selected from alkene and alkane；
In response to battery carrying out discharge and recharge in several cycles, in the surface of the TMCM negative electrodes room is generated；With
The room in the surface of the TMCM negative electrodes is filled with the additive agent electrolyte.
18. methods according to claim 17, wherein,
The solvent selected from water, carbonates, furans,Alkane, ether, ketone, ester, acid amides, acetic acid esters, siloxanes and their group
Close the group for constituting.
19. methods according to claim 17 or 18, wherein,
The group that the salt is constituted selected from following salt：AxCl、AxSO4、AxNO3、AxPO4、AxBr、AxI、AxAlO2、AxAc (acetic acid
Salt), AxPF6、AxBF6、AxClO4、AxAsF6、AxAlCl4、AxB5Cl5、AxCF3SO3、Ax(CF3SO2)2N and Ax(C2F5SO2)2N, its
In " A " selected from alkali and alkaline earth metal ions element constitute group.
20. methods according to any one of claim 17 to 19, wherein,
R includes the substituent in the group constituted selected from oxygen, silicon, fluorine, chlorine, phosphorus, aluminium, arsenic, selenium, bromine and combinations thereof.
21. methods according to any one of claim 17 to 20, wherein,
G and g is independently selected from the group being made up of alkane and alkene.
22. methods according to any one of claim 17 to 21, wherein,
Additive is to the percentage by weight (weight %) of solution in the range of 0.1 weight % to 50 weight %.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/320,352 US9620815B2 (en) | 2012-03-28 | 2014-06-30 | Electrolyte additives for transition metal cyanometallate electrode stabilization |
| US14/320,352 | 2014-06-30 | ||
| PCT/JP2015/003261 WO2016002194A1 (en) | 2014-06-30 | 2015-06-29 | Electrolyte additives for transition metal cyanometallate electrode stabilization |
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| CN107369846A (en) * | 2017-07-14 | 2017-11-21 | 北京理工大学 | Electrode slice and preparation method thereof and aluminium ion battery |
| CN108933234A (en) * | 2017-05-22 | 2018-12-04 | 鸿富锦精密工业（深圳）有限公司 | Electrode material, electrode slice, electrolyte and lithium ion secondary battery |
| CN113078416A (en) * | 2021-03-22 | 2021-07-06 | 电子科技大学 | Nano flower-shaped CoIn2S4Granule/graphite alkene complex modification's diaphragm |
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| AU2015213471B2 (en) | 2014-02-06 | 2018-02-01 | Gelion Technologies Pty Ltd | Gelated ionic liquid film-coated surfaces and uses thereof |
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| JP2010165674A (en) * | 2008-12-18 | 2010-07-29 | Equos Research Co Ltd | Electrolyte for sodium ion battery |
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| CN113078416A (en) * | 2021-03-22 | 2021-07-06 | 电子科技大学 | Nano flower-shaped CoIn2S4Granule/graphite alkene complex modification's diaphragm |
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