CN106848453A - Sodium-ion battery mends the method and sodium-ion battery of sodium - Google Patents
Sodium-ion battery mends the method and sodium-ion battery of sodium Download PDFInfo
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- CN106848453A CN106848453A CN201710142916.4A CN201710142916A CN106848453A CN 106848453 A CN106848453 A CN 106848453A CN 201710142916 A CN201710142916 A CN 201710142916A CN 106848453 A CN106848453 A CN 106848453A
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- sodium
- ion battery
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- ion
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 115
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000011734 sodium Substances 0.000 title claims abstract description 45
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 41
- 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 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 47
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 claims description 3
- 229960003351 prussian blue Drugs 0.000 claims description 3
- 239000013225 prussian blue Substances 0.000 claims description 3
- WDFGALOUDGKIOM-UHFFFAOYSA-N [Na].[V].P(O)(O)(O)=O Chemical compound [Na].[V].P(O)(O)(O)=O WDFGALOUDGKIOM-UHFFFAOYSA-N 0.000 claims 1
- 239000010949 copper Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical group 0.000 description 4
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910019463 NaV2 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020652 Na3V2 (PO4)3 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
-
- 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
Present invention is disclosed a kind of method that sodium-ion battery mends sodium, including：Metal simple-substance is mixed with sodium salt according to certain molar ratio, is added in positive electrode active materials as anode additive, prepare sodium-ion battery anode pole piece, and be assembled into battery；In the Battery formation stage, control initial charge voltage range makes metal simple-substance be reacted completely with sodium salt, discharges the sodium ion in the anode additive to cathode pole piece, participates in forming SEI films；Control battery cycle charge-discharge voltage range, makes sodium-ion battery enter normal discharge and recharge use state, and the metal simple-substance in additive is deposited in the battery in the form of metallic compound.The method that the sodium-ion battery that the present invention is provided compensates sodium ion, reduces the loss of active sodium ion in positive electrode, improves sodium-ion battery coulombic efficiency first, safe, practical and easy to operate.
Description
Technical field
The present invention relates to field of batteries, method and sodium-ion battery that sodium-ion battery mends sodium are especially related to.
Background technology
Sodium-ion battery operation principle is similar with lithium ion battery, and using sodium ion, embedding de- process is realized between both positive and negative polarity
Discharge and recharge.Compared with lithium ion battery, sodium-ion battery has had the advantage that：(1) sodium salt raw material rich reserves, price is low
It is honest and clean, compared ternary cathode material of lithium ion battery using ferrimanganic nickel-base anode material, cost of material reduction half；(2) due to
Sodium salt characteristic, it is allowed to use low concentration electrolyte (same concentration electrolytic solution, sodium salt electrical conductivity is higher than lithium electrolyte 20% or so)
Reduces cost；(3) sodium ion does not form alloy with aluminium, and negative pole can be using aluminium foil as collector, can further reduces cost
8% or so, reduce weight 10% or so；(4) because sodium-ion battery is without overdischarge characteristic, it is allowed to which sodium-ion battery discharges into zero
Volt.Sodium-ion battery energy density is more than 100Wh/kg, can be compared favourably with ferric phosphate lithium cell, but its cost advantage is substantially,
It is expected to replace traditional lead acid batteries in extensive energy storage.
Similar with lithium ion battery, sodium-ion battery can equally face the electrode material relatively low problem of coulombic efficiency first,
Sodium ion when the reason for coulombic efficiency is relatively low first is primarily due to battery initial charge from positive pole abjection can occur in negative pole
Reaction, forms SEI films or other side reactions occurs, and causes active sodium ion to lose.Cannot just have same so in battery discharge
Deng sodium ion from negative pole abjection return positive pole, cause the capacity of battery core relatively low.
Therefore, prior art could be improved.
The content of the invention
The main object of the present invention is to provide a kind of method that sodium-ion battery positive pole mends sodium, it is intended to solve sodium-ion battery
The low problem of coulombic efficiency first.
The present invention proposes a kind of method that sodium-ion battery positive pole mends sodium, including：
Metal simple-substance is mixed with sodium salt according to certain molar ratio, positive-active material is added to as anode additive
In material, sodium-ion battery anode pole piece is prepared, and be assembled into battery；
In the Battery formation stage, control initial charge voltage range makes metal simple-substance be reacted completely with sodium salt, and release is described
Sodium ion in anode additive participates in forming SEI films to cathode pole piece, reduces the loss of sodium ion in positive active material；
Control battery cycle charge-discharge voltage range, makes sodium-ion battery enter normal discharge and recharge use state, additive
In metal simple-substance deposited in the battery in the form of metallic compound.
Preferably, the metal simple-substance includes one or more in Fe, Co, Ni, Mo, Sn, Cu and Zn.
Preferably, the sodium salt includes the one kind in sodium oxide molybdena or vulcanized sodium.
Preferably, the mass ratio range of positive electrode shared by the anode additive that the metal simple-substance mixes with sodium oxide molybdena
It is 0.1-30wt%.
Preferably, when the molar ratio is according to metal simple-substance and sodium salt reaction generation stable metal compound and sodium ion
Reaction ratio determine.
Preferably, the chemical conversion stage initial charge voltage range is 0V to 4V.
Preferably, the battery cycle charge-discharge voltage range is 2.5V to 4V.
Present invention also offers a kind of sodium-ion battery, including anode pole piece, cathode pole piece, electrolyte and shell, institute
The additive package containing metal simple-substance Yu sodium salt in anode pole piece is stated, in Battery formation stage initial charge voltage range,
Metal simple-substance reacts completely with sodium salt.
Preferably, the active material of the anode pole piece includes vanadium phosphate sodium, fluorophosphoric acid vanadium sodium, cobalt acid sodium, sodium manganate, nickel
One or more in sour sodium and Prussian blue sodium.
Preferably, the both positive and negative polarity active material mol ratio is 1:1.02 to 1:1.2.
Beneficial effect of the present invention：The present invention by the positive electrode of sodium-ion battery add metal simple-substance and sodium salt,
And by the way that during Battery formation initial charge, control voltage scope makes metal simple-substance be reacted completely with sodium salt, release sodium from
Son forms SEI films making up sodium-ion battery negative pole in Battery formation or the sodium ion that is caused when there are other side reactions loses,
The loss of active sodium ion in positive electrode is reduced, sodium-ion battery coulombic efficiency first, the sodium ion that the present invention is provided is improved
The method that battery compensates sodium ion, it is safe, practical and easy to operate.
Brief description of the drawings
The sodium-ion battery positive pole of Fig. 1 one embodiment of the invention mends the method flow of sodium.
The realization of the object of the invention, functional characteristics and advantage will be described further referring to the drawings in conjunction with the embodiments.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Reference picture 1, the method that the sodium-ion battery positive pole that the embodiment of the present invention is proposed mends sodium, including：
S1：Metal simple-substance is mixed with sodium salt according to certain molar ratio, being added to positive pole as anode additive lives
In property material, sodium-ion battery anode pole piece is prepared, and be assembled into battery；
S2：In the Battery formation stage, control initial charge voltage range makes metal simple-substance be reacted completely with sodium salt, discharges institute
The sodium ion in anode additive is stated to cathode pole piece, participates in forming SEI films；
S3：Control battery cycle charge-discharge voltage range, makes sodium-ion battery enter normal discharge and recharge use state, addition
Metal simple-substance in agent is deposited in the battery in the form of metallic compound.
Sodium-ion battery can face the electrode material relatively low problem of coulombic efficiency first compared with lithium ion battery, equally,
Sodium ion when the reason for coulombic efficiency is relatively low first is primarily due to battery initial charge from positive pole abjection can occur in negative pole
Reaction, forms SEI films or other side reactions occurs, and causes active sodium ion to lose.
During liquid sodium-ion battery first charge-discharge, electrode material occurs instead with electrolyte on solid-liquid phase interface
Should, form one layer of passivation layer for being covered in electrode material surface.This passivation layer is a kind of boundary layer, with solid electrolyte
Feature, is electronic body, but is but the good conductor of sodium ion, and sodium ion can be freely embedded and de- by the passivation layer
Go out, therefore this layer of passivating film is referred to as solid electrolyte interface film (Solid Electrolyte Interface is referred to as：SEI).
Because part sodium ion participates in forming SEI or other side reactions, cannot just have in battery discharge equal sodium from
Son returns to positive pole from negative pole abjection, causes the capacity of battery core relatively low.The embodiment of the present invention is by the positive pole material in sodium-ion battery
Metal simple-substance and sodium salt are added in material, and setting suitable voltage range in chemical conversion makes metal simple-substance be reacted completely with sodium salt,
Sodium ion is obtained, and participates in form SEI films or other side reactions occur, make up the damage of active sodium ion in active material
Lose, so the first effect coulombic efficiency of sodium-ion battery problem.
Further, above-mentioned metal simple-substance includes one or more in Fe, Co, Ni, Mo, Sn, Cu and Zn.
Further, above-mentioned sodium salt includes the one kind in sodium oxide molybdena or vulcanized sodium.
The embodiment of the present invention is added to the mixing of metal simple-substance using sodium oxide molybdena as sodium-ion battery anode additive
Among positive electrode, the implementation process of the embodiment of the present invention is further described with the reaction of sodium oxide molybdena and metal simple-substance.
During initial charge, i.e. in the chemical conversion stage of battery core, there is reaction as follows, such as reaction equation (1), cancellation during chemical conversion
The low-voltage variation of battery core.In discharge regime, suitable stopping potential is selected, the back reaction of reaction (1) is reacted (2) cannot enter
OK, additive is with MOxForm deposit in the battery.
xNa2O+M→MOx+2xNa++2xe- (1)
MOx+2xNa++2xe-→xNa2O+M (2)
The sodium that be can be provided far more than normal sodium-ion battery positive material due to this sodium ion that can provide of reaction from
Son, this reaction is equivalent to additionally supplement sodium ion in battery initial charge, disappears when filling up battery initial charge generation SEI films
The sodium ion of consumption, and then improve the service efficiency of sodium-ion battery positive material.
Need to meet for the selection of metal simple-substance and sodium salt, both can occur redox reaction, and the electricity for reacting
There is certain interval band in the voltage range that position occurs residing for redox reaction with sodium-ion battery active material, both voltage
To be optimal without overlapping region, i.e., the sodium-ion battery that metal is less than normal work with the oxidizing potential of sodium oxide molybdena reaction is most for scope
Stopping potential high, sodium is electric less than the minimum cut-off of normal work sodium-ion battery with the reduction potential of this reactive metal oxide
Position.The sodium ion that the sodium ion that this metal and sodium oxide molybdena reaction are provided will be provided far more than common positive pole is considered simultaneously, i.e., singly
Position quality release sodium ion mole, equal quality release sodium ion it is more, be more conducive to improve the embodiment of the present invention in sodium from
Coulombic efficiency first, cycle performance of sub- battery etc., the performance of battery performance are more superior.
Further, the molar ratio is according to metal simple-substance and sodium salt reaction generation stable metal compound and sodium ion
When reaction ratio determine.As described above, Na2The molar ratio of O and metal simple-substance M is x:1, it is ensured that without metal simple-substance in battery
Residual, it is to avoid other are negatively affected to cause self discharge etc..
Further, the mass ratio model of positive electrode shared by the anode additive that the metal simple-substance mixes with sodium oxide molybdena
It is 0.1-30wt% to enclose.
The amount of additive is played battery performance directly influence, and additive capacity can not meet less fills up positive-active material
The loss of sodium ion in material, amount is more to cause excessive metallic compound residual in the battery, influence internal resistance of cell value and electrochemistry
The performance of performance.The embodiment of the present invention is optimized experiment to the mass ratio of positive electrode shared by additive, show compared with
The mass ratio range of positive electrode shared by the additive of good effect be 0.5-30wt%, battery show as first coulombic efficiency compared with
Height, electrochemistry capacitance is higher.
Further, the chemical conversion stage initial charge voltage range is 0V to 4V.
Further, the battery cycle charge-discharge voltage range is 2.5V to 4V.
The embodiment of the present invention is with Cu and Na2The implementation process of the embodiment of the present invention is further elaborated on as a example by O.Cu with
Na2The reaction equation of O is similar to reaction equation (1)：
Na2O+Cu→CuO+2Na++2e- (3)
Its back reaction reaction equation is similar to reaction equation (2)：
CuO+2Na++2e-→Na2O+Cu (4)
React the current potential of (3) between 0-3V, the current potential of reaction 4 is basic between 0-2V, reaction (4) in 2-3V substantially not
Release capacity.
Na3V2(PO4)3Typical charging and discharging curve, substantially all in 3.4V or so, current potential is less than 3.0V bases to charge and discharge potential
This does not show capacity.
Corresponding reaction equation is respectively：
Na3V2(PO4)3→2Na++2e-+NaV2(PO4)3 (5)
This equation correspondence charging process, voltage ascending curve；
2Na++2e-+NaV2(PO4)3→Na3V2(PO4)3 (6)
This equation correspondence discharge process, voltage falloff curve.
With vanadium phosphate sodium as positive pole, hard carbon is that negative pole assembles sodium-ion battery, and the operating voltage range of battery is designed as
2.7-3.9V.Cu and Na is added in the embodiment of the present invention in positive electrode2O carries out benefit sodium as additive.In Battery formation
Stage, voltage begins to ramp up from 0V, at this moment can preferentially react (3), until Cu and Na2O reacts there is provided sodium ion completely.
Can rise as formation process carries out voltage, until reaching 3.4V, reaction (5) takes place, positive electrode Na3V2(PO4)3Open
Begin normal removing sodium.
During to first time charging complete 3.9V, Cu and Na2O and Na3V2(PO4)3In Na ions all can be completely out.Then
Start to discharge for the first time, now preferentially react (6).With when electric discharge carries out voltage drops to 2.7V, battery discharge is reached
The lower voltage limit of terminal profile, battery discharge terminates.Because the voltage for reacting (4) is interval in 0-2V, this reaction will not occur, institute
After completing chemical conversion, additive is then deposited in the battery in the form of CuO.
In follow-up circulation, battery works in 2.7-3.9V voltage ranges, and the reaction of generation is (5) and (6) two
Reaction, (3) and (4) are not up to voltage range, and reaction does not occur.What is showed in the battery is exactly CuO as nonactive thing
Matter is remained among the positive pole of battery.This specific embodiment also further illustrates the quality of positive electrode shared by optimization additive
The importance of proportion.
In discharge regime, reaction is controlled to occur by selecting suitable stopping potential.As described above reaction (4) with it is anti-
Answer (6) to there is an interpotential interval band, be all suitable blanking voltage scope in this intervallum interval.Even if positive electrode
Electric discharge is complete and CuO does not react also with sodium ion.
The sodium ion that Ni metal and sodium oxide molybdena reaction are provided in the embodiment of the present invention will be far more than common positive electrode Na3V2
(PO4)3The sodium ion for being provided.It is above-mentioned both to generate sodium ion, Na3V2(PO4)3The middle sodium ion theoretical amount that can be provided is about
It is 117mAh/g, Cu and Na2The sodium ion that O theories can be provided is about 425mAh/g.The sodium that the latter can provide under phase homogenous quantities from
Son is much larger than the former.So when negative pole chemical conversion needs to consume more sodium ion, by adding Cu and Na2O can be effectively real
The effect of sodium ion is now supplemented, the coulombic efficiency first of battery is improved.
In addition, Ni metal is electric less than the sodium ion of normal work with the oxidizing potential of sodium oxide molybdena reaction in the embodiment of the present invention
Pond highest stopping potential, that is, react the current potential (3.0-3.9V) of the current potential (0-3V) less than reaction (5) of (3), can avoid completely anti-
(5) situation that terminating reaction (3) does not terminate also of answering.Sodium is reaction (4) with the reduction potential of this reactive metal oxide
Current potential (0-2V), less than the minimum stopping potential 2.7V of normal sodium-ion battery.
According to particular condition in use, above-mentioned Ni metal can be replaced Mo, Sn, Co or Zn, Na2O can be replaced S, and institute is right
The MoS for answering2、SnS2,、CoS23V is less than with the charging potential of ZnS, discharge potential is less than 2.5V, and these sulfide can be replaced
Above-mentioned CuO, and keep the normal charge and discharge potential of sodium-ion battery constant.
It is above-mentioned just for positive electrode Na3V2(PO4)3Be the sodium-ion battery of example, the sodium of different positive electrodes from
Sub- cell cutoff current potential is otherwise varied.For example when positive electrode is Prussian blue series material, blanking voltage is 2.0V.
The embodiment of the present invention additionally provides a kind of sodium-ion battery, including anode pole piece, cathode pole piece, electrolyte and outer
Shell, the additive package containing metal simple-substance Yu sodium salt in the anode pole piece, in Battery formation stage initial charge voltage model
In enclosing, metal simple-substance reacts completely with sodium salt.
Further, the active material of the anode pole piece include vanadium phosphate sodium, fluorophosphoric acid vanadium sodium, cobalt acid sodium, sodium manganate,
Nickel acid sodium and Prussian blue sodium in one or more.
Further, the positive and negative electrode active material mol ratio is 1:1.02 to 1:1.2.
Sodium-ion battery electrolyte is the sodium perchlorate organic solution of 1mol/L, and solute is sodium perchlorate, solvent include EC,
One or more in PC, DEC and DMC etc..
Above-mentioned sodium-ion battery with hard carbon as negative material, and according to negative material, conductive agent (SuperP conductive blacks)
And the quality proportioning of binding agent PVDF (Polyvinylidene Fluoride polyvinyladine florides) is 0.94:0.04:0.02 enters
Row batch mixing, coating prepares cathode pole piece；With Na3V2(PO4)3Be positive electrode, and by positive electrode, conductive agent, binding agent matter
Amount proportioning is 0.95:0.03:0.02 carries out batch mixing, and coating prepares anode pole piece, and the positive and negative electrode active material mol ratio is
1:1.05.Soft pack cell is prepared with the positive and negative electrode pole piece coiling, electrolyte uses the NaClO of 1M4/ PC, is assembled into sodium ion
Battery.The Cu and Na of accounting positive electrode active materials quality 10wt% are added in positive electrode2The mixed powder of O, in Battery formation
Stage, voltage begins to ramp up from 0V, ends to during 3.9V；Discharge cut-off voltage is controlled for 2.7V, the normal discharge and recharge of further battery
Pressure scope is 2.7-3.9V, and it is 85% that sodium-ion battery shows as coulombic efficiency first, and capacity is 1100mAh.
The additive without any metal and sodium salt is prepared with same manufacture craft, i.e., does not use the embodiment of the present invention
Benefit sodium technology, ibid, but the coulombic efficiency first of gained sodium-ion battery is 73% to Battery formation technique, and capacity is
1003mAh。
The embodiment of the present invention by adding metallic copper and sodium oxide molybdena in the positive electrode of sodium-ion battery, and by electricity
During initial charge in the chemical conversion of pond, to 3.9V, discharge voltage range 2.7 makes metal to control charge voltage range 0 to 3.9V
Elemental copper is reacted completely with sodium oxide molybdena, release sodium ion with make up sodium-ion battery negative pole in Battery formation formed SEI films or its
The sodium ion caused during its side reaction loses, and reduces the loss of active sodium ion in positive electrode, improves sodium-ion battery first
Coulombic efficiency, the method that the sodium-ion battery provided in the embodiment of the present invention mends sodium, to the chemical property of sodium-ion battery
Performance improves significantly effect, and easy to operate, without potential safety hazard in use.
The preferred embodiments of the present invention are the foregoing is only, the scope of the claims of the invention, every utilization is not thereby limited
Equivalent structure or equivalent flow conversion that description of the invention and accompanying drawing content are made, or directly or indirectly it is used in other correlations
Technical field, be included within the scope of the present invention.
Claims (10)
1. a kind of method that sodium-ion battery mends sodium, it is characterised in that including：
Metal simple-substance is mixed with sodium salt according to certain molar ratio, positive electrode active materials are added to as anode additive
In, sodium-ion battery anode pole piece is prepared, and be assembled into battery；
In the Battery formation stage, control initial charge voltage range makes metal simple-substance be reacted completely with sodium salt, discharges the positive pole
Sodium ion in additive participates in forming SEI films to cathode pole piece；
Control battery cycle charge-discharge voltage range, makes sodium-ion battery enter normal discharge and recharge use state, in additive
Metal simple-substance is deposited in the battery in the form of metallic compound.
2. the method that sodium-ion battery according to claim 1 mends sodium, it is characterised in that the metal simple-substance include Fe,
One or more in Co, Ni, Mo, Sn, Cu and Zn.
3. the method that sodium-ion battery according to claim 1 mends sodium, it is characterised in that the sodium salt include sodium oxide molybdena or
One kind in vulcanized sodium.
4. the method that sodium-ion battery according to claim 3 mends sodium, it is characterised in that the metal simple-substance and sodium oxide molybdena
The mass ratio range of positive electrode shared by the anode additive of mixing is 0.1-30wt%.
5. the method that sodium-ion battery according to claim 1 mends sodium, it is characterised in that the molar ratio is according to metal
Reaction ratio when simple substance is with sodium salt reaction generation stable metal compound and sodium ion determines.
6. the method that sodium-ion battery according to claim 1 mends sodium, it is characterised in that the chemical conversion stage initial charge
Voltage range is 0V to 4V.
7. the method that sodium-ion battery according to claim 1 mends sodium, it is characterised in that the battery cycle charge-discharge electricity
Pressure scope is 2.5V to 4V.
8. a kind of sodium-ion battery, including anode pole piece, cathode pole piece, electrolyte and shell, it is characterised in that the positive pole
Additive package containing metal simple-substance Yu sodium salt in pole piece, in Battery formation stage initial charge voltage range, metal list
Matter is reacted completely with sodium salt.
9. sodium-ion battery according to claim 8, it is characterised in that the active material of the anode pole piece includes phosphoric acid
Vanadium sodium, fluorophosphoric acid vanadium sodium, cobalt acid sodium, sodium manganate, nickel acid sodium and Prussian blue sodium in one or more.
10. sodium-ion battery according to claim 8, it is characterised in that the both positive and negative polarity theoretical specific capacity proportioning is 1:
1.02 to 1:1.2.
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| CN108336301A (en) * | 2018-02-06 | 2018-07-27 | 哈尔滨工业大学 | A kind of high-performance sodium-ion battery cathode and preparation method thereof |
| CN109585844A (en) * | 2018-11-26 | 2019-04-05 | 中南大学 | A kind of benefit sodium positive electrode active materials, positive electrode, sodium-ion battery and its preparation and application |
| CN109786660A (en) * | 2018-12-17 | 2019-05-21 | 中国电子科技集团公司第十八研究所 | Sodium ion battery electrode capable of carrying out positive electrode pre-sodium treatment |
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