CN108878780A - Sodium-ion battery cathode mends sodium method and sodium-ion battery - Google Patents
Sodium-ion battery cathode mends sodium method and sodium-ion battery Download PDFInfo
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- CN108878780A CN108878780A CN201810590050.8A CN201810590050A CN108878780A CN 108878780 A CN108878780 A CN 108878780A CN 201810590050 A CN201810590050 A CN 201810590050A CN 108878780 A CN108878780 A CN 108878780A
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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Abstract
Present invention discloses a kind of sodium-ion battery cathode to mend sodium method and sodium-ion battery, including：In an inert atmosphere, solid metallic sodium is melted at a certain temperature, obtains liquid metal sodium；The liquid metal sodium is uniformly made an addition to the surface of negative electrode tab, so that the liquid metal sodium penetrates into the gap between the negative electrode material of the negative electrode tab；The dry negative electrode tab.Sodium-ion battery cathode provided by the invention mends sodium method and sodium-ion battery, by in an inert atmosphere, the surface of negative electrode tab is uniformly made an addition to after metallic sodium is melted, it simply and efficiently realizes and benefit sodium is carried out to sodium-ion battery, solving the problems, such as sodium-ion battery, coulombic efficiency is low for the first time, the energy density for improving sodium-ion battery entirety, to sodium-ion battery also without negative effect.
Description
Technical field
The present invention relates to sodium-ion battery technical fields, and in particular to a kind of sodium-ion battery cathode mend sodium method and sodium from
Sub- battery.
Background technique
In lithium resource in the case where limited and higher cost, sodium-ion battery is due to at low cost, rich reserves, distribution
Extensive feature will become the ideal replacer of lithium ion battery.The working principle of sodium-ion battery is similar with lithium ion battery,
Using sodium ion, embedding de- process realizes charge and discharge between positive and negative anodes, therefore sodium-ion battery is asked there is also coulombic efficiency for the first time is low
Topic can be reacted in cathode from the sodium ion of anode abjection when mainly being charged due to sodium-ion battery first lap, form SEI
Other side reactions occur for film, and active sodium ion is caused to lose.Can not just there be same sodium when sodium-ion battery discharges in this way
Ion is deviate to return to anode from cathode, and the performance of material can not play completely, causes the capacity of battery relatively low.
By carrying out benefit sodium to sodium-ion battery, the sodium-ion battery low problem of coulombic efficiency for the first time can solve.It is existing
Benefit sodium method about sodium-ion battery has following several：1, metal is mixed with sodium oxide molybdena, is added just collectively as additive
Pole material discharges sodium ion therein by the way of electrochemistry, carries out benefit sodium to sodium-ion battery.2, metallic sodium is dissolved in
Then organic solvent will contain the sprinkling of sodium organic solution or be added dropwise in negative electrode tab surface, and go back the sodium ion in organic sodium solution
Original is at metallic sodium and is embedded in negative electrode tab, completes the benefit sodium to sodium-ion battery.
The above method 1 haves the shortcomings that inefficient, and electrochemical method can discharge part sodium ion, but can also be remaining
Some inactive impurity, cause the reduction of sodium-ion battery integral energy density.The above method 2 there are process it is more complex lack
Point, and organic solvent is introduced in cathode, in the sodium-ion battery production phase it is possible that organic substance residues are in cathode, from
And make the penalty of sodium-ion battery.
Summary of the invention
The main object of the present invention is to provide a kind of sodium-ion battery cathode benefit sodium method, and it is real to pass through the method being simple and efficient
Benefit sodium now is carried out to sodium-ion battery, solving the problems, such as sodium-ion battery, coulombic efficiency is low for the first time.
The present invention proposes that a kind of sodium-ion battery cathode mends sodium method, includes the following steps：
In an inert atmosphere, solid metallic sodium is melted under specified for temperature ranges, obtains liquid metal sodium；
The liquid metal sodium of specified amount is uniformly made an addition to the surface of negative electrode tab, so that the liquid metal sodium is uniform
It penetrates into the gap between the negative electrode material of the negative electrode tab；
The dry negative electrode tab.
Preferably, it is described in an inert atmosphere, solid metallic sodium is melted under specified for temperature ranges, obtains liquid metal
The step of sodium includes：
The inert gas of specified amount is inputted into melting tank, and opens vacuum heater and is heated to specify by the melting tank
Temperature range melts the solid metallic sodium, obtains liquid metal sodium.
Preferably, the surface that the liquid metal sodium of specified amount is uniformly made an addition to negative electrode tab, so that the liquid
State metallic sodium uniformly penetrates into the step in the gap between the negative electrode material of the negative electrode tab, including：
The liquid metal sodium is delivered to and is placed in the negative electrode tab in retractable volume system, by controlling the liquid metal
The speed that sodium is squeezed out from extrusion die, amount and the position of the liquid metal sodium are added in control in the negative electrode tab, so that institute
Liquid metal sodium is stated uniformly to penetrate into the gap between the negative electrode material of the negative electrode tab.
Preferably, the inert gas that the inert atmosphere uses includes one or both of argon gas, helium.
Preferably, the specified for temperature ranges includes 98 DEG C to 200 DEG C.
Preferably, the range of the liquid metal sodium of the specified amount is the negative electrode material total capacity of the negative electrode tab
1% to 25%.
Preferably, the negative electrode material of the negative electrode tab includes hard carbon material, sulfide, oxide, metal simple-substance and conjunction
One or more of golden material.
The present invention also provides a kind of sodium-ion batteries, mend sodium method including the use of above-mentioned sodium-ion battery cathode and are made
Negative electrode tab.
It preferably, further include positive plate, the positive electrode of the positive plate includes vanadium phosphate sodium, fluorophosphoric acid vanadium sodium, cobalt acid
One or more of sodium, sodium manganate, nickel acid sodium and prussian blue material.
Preferably, the positive and negative anodes theoretical specific capacity proportion is 1:1.03 to 1:1.2.
A kind of sodium-ion battery cathode provided by the invention mends sodium method and sodium-ion battery, by an inert atmosphere,
Solid metallic sodium fusion is melted, the liquid metal sodium after melting is uniformly made an addition to the surface of negative electrode tab, the metallic sodium after melting is in
Liquid condition can be embedded into the gap between the negative electrode material of negative electrode tab, so that metallic sodium is uniformly distributed in cathode
In piece.The present invention does not have the inactive impurity such as metal oxide finally and remains in anode, and it is organic not need configuration metal yet
Sodium solution passes through the liquid metal sodium obtained after directly melting solid metallic sodium fusion to cause to have organic substance residues in cathode
The surface of negative electrode tab is uniformly made an addition to, simply and efficiently realizes and benefit sodium is carried out to sodium-ion battery, solve sodium-ion battery first
The low problem of secondary coulombic efficiency improves the utilization rate and whole energy density of sodium-ion battery active material, to sodium ion
Battery is also without negative effect.
Detailed description of the invention
Fig. 1 is that the sodium-ion battery cathode of one embodiment of the invention mends the method flow schematic diagram of sodium.
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.
Referring to Fig.1, a kind of sodium-ion battery cathode of one embodiment of the invention mends sodium method, including：
S1：In an inert atmosphere, solid metallic sodium is melted at a certain temperature, obtains liquid metal sodium.
S2：The liquid metal sodium of specified amount is uniformly made an addition to the surface of negative electrode tab, so that the liquid metal sodium
It uniformly penetrates into the gap between the negative electrode material of the negative electrode tab.
S3：The dry negative electrode tab.
Wherein, above-mentioned step S1~S3 is carried out in an inert atmosphere.According to the fusing point (97.81 of metallic sodium
DEG C), setting one is greater than 97.81 DEG C of specified for temperature ranges, so that at this range of temperature can be effectively by solid metallic
Sodium is melt into the metallic sodium state of liquid；In addition, the liquid metal sodium after the melting of addition is all effective electroactive material,
The mode of addition can be sprinkling or dropwise addition, just can control the liquid for being added to negative electrode tab surface by the time sprayed or be added dropwise
The amount of metallic sodium.Negative electrode tab itself is made of negative electrode material, conductive agent, binder etc., and microcosmic upper negative electrode tab is porous gap knot
Structure, i.e., between negative electrode active material particle there are between gap or negative electrode active material particle and conductive agent there is also gap,
The presence in these gaps is for retaining electrolyte, so that the sodium ion in sodium-ion battery is transported back and forth between positive and negative anodes
It is dynamic, realize the charge and discharge cycles of sodium-ion battery.When adding liquid metal sodium toward the surface of negative electrode tab, since liquid metal sodium has
There is the mobility of liquid, then liquid metal sodium can penetrate into automatically in porous gap structure, pay attention to being added in sprinkling or dropwise addition
The position distribution of the liquid metal sodium added can be such that sodium is evenly distributed in negative electrode tab, realize and uniformly mend sodium, prevent negative electrode tab
Sodium and deformation are analysed, improves the coulombic efficiency for the first time of sodium-ion battery, and then improve the energy density of sodium-ion battery.
The working principle of sodium-ion battery is similar with lithium ion battery, can equally face electrode material for the first time coulombic efficiency compared with
Low problem, can be from the sodium ion of anode abjection when the lower reason of coulombic efficiency is primarily due to battery initial charge for the first time
Cathode reacts, and forms SEI film or other side reactions occur, active sodium ion is caused to lose.
During liquid sodium-ion battery first charge-discharge, electrode material and electrolyte occur instead on solid-liquid phase interface
It answers, forms 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 the good conductor of sodium ion, and sodium ion can be freely embedded in and be taken off by the passivation layer
Out, therefore this layer of passivating film is known as solid electrolyte interface film (Solid Electrolyte Interface abbreviation：SEI).By
In part, sodium ion participates in forming SEI film or other side reactions, can not just have same sodium ion in battery discharge from negative
Pole abjection returns to anode, causes the capacity of battery core relatively low.
The embodiment of the present invention uniformly adds the liquid after the melting of specified amount by the surface of the negative electrode tab to sodium-ion battery
State metallic sodium, due to liquid have mobility, then the metallic sodium of liquid condition can penetrate into automatically negative electrode tab negative electrode material it
Between gap in, to make up the loss of active sodium ion in active material, and then solve the first effect library of sodium-ion battery
The problem of human relations efficiency.
Further, above-mentioned S1 step includes：
S10：The inert gas of specified amount is inputted into melting tank, and opens vacuum heater and is heated to the melting tank
Specified for temperature ranges melts the solid metallic sodium, obtains liquid metal sodium.
Wherein, melting tank and vacuum heater are set in specific benefit sodium device, and melting tank belongs to sealing device, are used for
Melt solid metallic sodium, volume can with depending on according to actual conditions, and the material for melting tank be corrosion-resistant, high temperature resistant and not with melting
Chromium-austenitic stainless steel material of sodium reaction；Vacuum heater is used for heating melting tank, to melt solid metallic sodium, thus
Obtain liquid metal sodium.
Further, above-mentioned S2 step, including：
S20：The liquid metal sodium is delivered to and is placed in the negative electrode tab in retractable volume system, by controlling the liquid
The speed that metallic sodium is squeezed out from extrusion die, control are added amount and the position of the liquid metal sodium in the negative electrode tab, are made
The liquid metal sodium is obtained uniformly to penetrate into the gap between the negative electrode material of the negative electrode tab.
Wherein, retractable volume system and extrusion die are also disposed in above-mentioned benefit sodium device, due to the liquid obtained after melting
State metallic sodium and negative electrode tab are all being mended in sodium device, therefore liquid gold is added on the surface for the negative electrode tab being placed in retractable volume system
Belong to the influence that sodium not will receive external environment, will not cause damages to operator and external environment, while also facilitating operation.
Further, the inert gas that the inert atmosphere uses includes one or both of argon gas, helium.
Under an inert atmosphere, the oxygen in air and moisture etc. can be isolated, and avoid the active gold of chemical property
Belong to sodium some chemical reactions occur in melting process and generate some impurity.
In addition, due to by melting after metallic sodium be liquid, therefore make an addition to all be on negative electrode tab surface liquid metal
Sodium is not in have solid metal sodium floats in air, ensure that the entire safety for mending sodium process.
Further, the specified for temperature ranges includes 98 DEG C to 200 DEG C.
Wherein, the fusing point of metallic sodium is 97.81 DEG C, and solid metallic sodium is carried out under 98 DEG C to 200 DEG C of temperature range
Melting is used for heating melting tank by vacuum heater, so that temperature range controls in 98 DEG C to 200 DEG C, thus effectively
Solid metallic sodium is melt into liquid metal sodium.
Further, the range of the liquid metal sodium of the specified amount is the negative electrode material total capacity of the negative electrode tab
1% to 25%.
Wherein, the cathode sodium supplementing amount of sodium-ion battery is calculated according to the capacitance loss of required supplement, commonly required addition
The amount of liquid metal sodium is the 1% to 25% of the negative electrode material total capacity of negative electrode tab；By being fitted to sodium-ion battery cathode
The benefit sodium of amount, can make up for it the loss of active sodium ion in active material, and then solve the first effect library of sodium-ion battery
The problem of human relations efficiency.
Further, the negative electrode material of the negative electrode tab include hard carbon material, sulfide, oxide, metal simple-substance and
One or more of alloy material.
Wherein, preferably hard carbon material is as negative electrode material used in the embodiment of the present invention.Hard carbon material also referred to as can not
Graphitized amorphous carbon is that comprehensive performance is best in current numerous negative electrode materials.It is hard carbon material stable structure, with higher
Capacity, charge and discharge circulation life are long, have a safety feature and presoma materials are extensive, will be in the commercialization of the following sodium-ion battery
It plays an important role.Although passing through this there is also the problem that coulombic efficiency for the first time is low when hard carbon material is as electrode material
The sodium ion that invention provides, which mends sodium method, can effectively improve the coulombic efficiency for the first time of sodium-ion battery, thus can also be fine
The ground comprehensive performance outstanding using hard carbon material, to achieve the effect that the overall performance for mentioning sodium-ion battery.
Further, the hard carbon material is resin carbon and/or carbon black.
Further, the carbon black is conductive black.
The present invention also provides a kind of sodium-ion batteries, mend sodium method including the use of above-mentioned sodium-ion battery cathode and are made
Negative electrode tab.
It further, further include anode, the positive electrode of the positive plate includes vanadium phosphate sodium, fluorophosphoric acid vanadium sodium, cobalt acid
One or more of sodium, sodium manganate, nickel acid sodium and prussian blue material.
Wherein, preferably prussian blue material is as positive electrode used in the embodiment of the present invention.Prussian blue is a kind of
Ancient blue dyes is used to glazing earliest and does oil painting dyestuff, in terms of being applied to catalysis and battery later.It is Prussian blue
And its derivative opens frame structure with special, crystals stress is small, stable structure, suitable for the fast of alkali metal ion
Speed migration, may make current density to significantly improve, and good cycling stability.
Further, the positive and negative anodes theoretical specific capacity proportion is 1:1.03 to 1:1.2.
Wherein, in embodiments of the present invention, due to existing through the liquid metal sodium after being melted toward negative electrode tab addition, so that
Battery has additional sodium ion supplement, therefore can more optimize in the positive and negative pole material proportion for designing battery.The list of battery
Plane product capacity of negative plates is known as CB value with respect to the ratio of positive electrode capacity, and CB value requires to be greater than the bigger analysis sodium of 1, CB value in normal battery
Risk it is lower, general range be 1.05 to 1.2 between, the design of sodium-ion battery also to follow this rule.But due to
Sodium ion cathode head effect is very low, and positive-active sodium ion is caused to lose, therefore the battery capacity meeting of performance for not carrying out mending sodium is very low,
For the loss for making up negative electrode active sodium, CB value is only reduced, such as CB value is dropped to close to 1, can actually there is safety in this way
Hidden danger has the risk of analysis sodium.And the lithium ion battery of sodium is mended for progress of the invention, CB value can be increased without will affect
The capacity of lithium ion battery plays, still the range for the CB value for mend the sodium-ion battery of sodium can be designed as 1.03
To 1.2, to improve the safety of lithium ion battery.
The preparation flow of the sodium-ion battery of the embodiment of the present invention is as follows：
It will be passed through as the above-mentioned negative electrode tab operated through overfill sodium and the positive plate as made from prussian blue material and diaphragm
The mode of winding is assembled into battery core, later by closedtop, fluid injection (sodium salt concentration is 1mol/L), standing, chemical conversion, shaping and degasification
Etc. processes, sodium-ion battery is prepared.
Wherein, in the negative electrode tab operated through overfill sodium, sodium supplementing amount is controlled, that is, the range of the liquid metal sodium added is upper
State the 1% to 25% of the negative electrode material total capacity of negative electrode tab；In addition, control positive plate as made from prussian blue material and warp
The capacity ratio of the negative electrode tab of overfill sodium operation is 1:1.03 to 1:1.2.
The following are specific embodiments：
Embodiment 1：
A kind of method for mending sodium the present embodiment provides sodium-ion battery cathode exists solid metallic sodium in argon atmosphere
It is melted at a temperature of 98 DEG C, obtains liquid metal sodium, liquid metal sodium is sprayed or is added dropwise in the surface (cathode of negative electrode tab later
Negative electrode material in piece is conductive black) so that liquid metal sodium penetrates into the gap between conductive black, control the liquid of addition
The amount of state metallic sodium is the 1% of conductive black total capacity, i.e., the embedding sodium amount in conductive black is the 1% of conductive black total capacity,
Then negative electrode tab is dried, completes to mend sodium operation.
By the capacity of the negative electrode tab operated in the positive plate as made from prussian blue material and the present embodiment through overfill sodium
Burden control is 1:1.03, it is assembled into battery core by the mode of winding with diaphragm later, using closedtop, fluid injection (sodium salt concentration
For processes such as 1mol/L), standing, chemical conversion, shaping and degasification, sodium-ion battery 1 is prepared, the number of battery is denoted as A1.
Embodiment 2：
In helium atmosphere, by solid metallic sodium 200 DEG C at a temperature of melt, liquid metal sodium is obtained, later by liquid
The sprinkling of state metallic sodium is added dropwise in the surface (negative electrode material in negative electrode tab is conductive black) of negative electrode tab, so that liquid metal sodium
It penetrates into the gap between conductive black, the amount for controlling the liquid metal sodium of addition is the 25% of conductive black total capacity, that is, is led
Embedding sodium amount in electric carbon black is the 25% of conductive black total capacity, then dries negative electrode tab, completes to mend sodium operation.
By the capacity of the negative electrode tab operated in the positive plate as made from prussian blue material and the present embodiment through overfill sodium
Burden control is 1:1.2, it is assembled into battery core by the mode of winding with diaphragm later, (sodium salt concentration is using closedtop, fluid injection
1mol/L), the processes such as standing, chemical conversion, shaping and degasification, are prepared sodium-ion battery 2, the number of battery is denoted as A2.
Embodiment 3：
In argon atmosphere, by solid metallic sodium 130 DEG C at a temperature of melt, liquid metal sodium is obtained, later by liquid
The sprinkling of state metallic sodium is added dropwise in the surface (negative electrode material in negative electrode tab is conductive black) of negative electrode tab, so that liquid metal sodium
It penetrates into the gap between conductive black, the amount for controlling the liquid metal sodium of addition is the 5% of conductive black total capacity, i.e., conductive
Embedding sodium amount in carbon black is the 5% of conductive black total capacity, then dries negative electrode tab, completes to mend sodium operation.
By the capacity of the negative electrode tab operated in the positive plate as made from prussian blue material and the present embodiment through overfill sodium
Burden control is 1:1.09, it is assembled into battery core by the mode of winding with diaphragm later, using closedtop, fluid injection (sodium salt concentration
For processes such as 1mol/L), standing, chemical conversion, shaping and degasification, sodium-ion battery 3 is prepared, the number of battery is denoted as A3.
Embodiment 4：
In argon atmosphere, by solid metallic sodium 150 DEG C at a temperature of melt, liquid metal sodium is obtained, later by liquid
The sprinkling of state metallic sodium is added dropwise in the surface (negative electrode material in negative electrode tab is conductive black) of negative electrode tab, so that liquid metal sodium
It penetrates into the gap between conductive black, so that the amount of the liquid metal sodium of addition is the 10% of conductive black total capacity, that is, leads
Embedding sodium amount in electric carbon black is the 10% of conductive black total capacity, then dries negative electrode tab, completes to mend sodium operation.
By the capacity of the negative electrode tab operated in the positive plate as made from prussian blue material and the present embodiment through overfill sodium
Burden control is 1:1.13, it is assembled into battery core by the mode of winding with diaphragm later, using closedtop, fluid injection (sodium salt concentration
For processes such as 1mol/L), standing, chemical conversion, shaping and degasification, sodium-ion battery 4 is prepared, the number of battery is denoted as A4.
Embodiment 5：
In helium atmosphere, by solid metallic sodium 170 DEG C at a temperature of melt, liquid metal sodium is obtained, later by liquid
The sprinkling of state metallic sodium is added dropwise in the surface (negative electrode material in negative electrode tab is conductive black) of negative electrode tab, so that liquid metal sodium
It penetrates into the gap between conductive black, so that the amount of the liquid metal sodium of addition is the 17% of conductive black total capacity, that is, leads
Embedding sodium amount in electric carbon black is the 17% of conductive black total capacity, then dries negative electrode tab, completes to mend sodium operation.
By the capacity of the negative electrode tab operated in the positive plate as made from prussian blue material and the present embodiment through overfill sodium
Burden control is 1:1.17, it is assembled into battery core by the mode of winding with diaphragm later, using closedtop, fluid injection (sodium salt concentration
For processes such as 1mol/L), standing, chemical conversion, shaping and degasification, sodium-ion battery 5 is prepared, the number of battery is denoted as A5.
Comparative example 1：
The preoperative negative electrode tab of sodium will be mended, and (negative electrode tab i.e. without overfill sodium, the negative electrode material in negative electrode tab are conductive charcoal
It is black), and the capacity of the negative electrode tab operated by the positive plate as made from prussian blue material in the present embodiment and without overfill sodium
Burden control is 1:1.03, it is assembled into battery core by the mode of winding with diaphragm later, using closedtop, fluid injection (sodium salt concentration
For processes such as 1mol/L), standing, chemical conversion, shaping and degasification, sodium-ion battery 6 is prepared, the number of battery is denoted as B1.
Comparative example 2：
Concentration is 1M's in argon atmosphere by a kind of method that the present embodiment mends sodium using sodium-ion battery negative electrode tab
The hexane solution of normal-butyl sodium is sprayed on the surface (active material in negative electrode tab is conductive black) of negative electrode tab, makes normal-butyl
Sodium ion in sodium solution penetrates into negative electrode tab, so that the embedding sodium amount in conductive black is the 5% of conductive black total capacity, then
Dry negative electrode tab is completed to mend sodium operation.
By the capacity of the negative electrode tab operated in the positive plate as made from prussian blue material and the present embodiment through overfill sodium
Burden control is 1:1.03, it is assembled into battery core by the mode of winding with diaphragm later, using closedtop, fluid injection (sodium salt concentration
For processes such as 1mol/L), standing, chemical conversion, shaping and degasification, sodium-ion battery 7 is prepared, the number of battery is denoted as B2.
Comparative example 3：
The present embodiment is using a kind of method for mending sodium to sodium-ion battery anode, and steps are as follows：
Using hard carbon material as negative electrode material, and (gather inclined fluorine according to negative electrode material, conductive agent (conductive black) and binder
Second is dilute) quality proportioning be 0.94:0.04:0.02 carries out mixing, and coating prepares cathode pole piece；It is positive material with vanadium phosphate sodium
Material, and be 0.95 by the quality proportioning of positive electrode, conductive agent, binder:0.03:0.02 carries out mixing, coating preparation anode
Pole piece, the positive and negative electrode active material mol ratio are 1:1.05.Soft pack cell is prepared with the positive and negative electrode pole piece coiling, electricity
Solve the NaClO that liquid uses 1M4/ PC, is assembled into sodium-ion battery 8, and the number of battery is denoted as B3.Accounting is being added just in positive electrode
The copper of pole active material quality 10wt% and the mixed powder of sodium oxide molybdena, in the Battery formation stage of sodium-ion battery 4, voltage from
0V is begun to ramp up, until ending when 3.9V, control discharge cut-off voltage is 2.7V.
In 25 DEG C of environment by following process respectively to number be A1-A5 and the sodium-ion battery of B1-B3 carry out capacity survey
Examination：3min is stood first；Then it is charged with the charging current constant-current charge of 0.5C to 4.2V, then constant-voltage charge to 0.05C
Capacity AGC0；Stand 3min；Discharge capacity D0 for the first time is obtained with the discharge current constant-current discharge of 0.5C to 2.5V again；Stand 3min
Volume test is completed later；The coulombic efficiency for the first time of calculating sodium-ion battery is later：D0/ (ICC0+AGC0), acquired results show
In table 1.
In 25 DEG C of environment with the charge-discharge magnification of 0.5C/0.5C respectively to number be A1-A5 and the battery of B1-B3 carry out
Cycle performance is tested, and the capacity after initial charge is C0, while recording the capacity C 500 of battery after 500 circulations, is calculated
Capacity retention ratio C500/C0 of the battery after 500 circulations, acquired results are shown in table 1.
Table 1：The volume test result of sodium-ion battery and for the first time coulombic efficiency.
By table 1 it can be concluded that, sodium-ion battery 1~5 obtained by benefit sodium is carried out by the way of melting metallic sodium and (is compiled
Number be A1~A5) compared to without overfill sodium operate made of sodium-ion battery 6 (number B1), coulombic efficiency obtains for the first time
It greatly improves, and the utilization rate and whole energy density of sodium-ion battery active material, cycle performance greatly improved
It is improved.In addition, then will contain the sprinkling of sodium organic solution with using metallic sodium is dissolved in organic solvent or be added dropwise in negative
Pole piece, so that the sodium ion in organic sodium solution is reduced into metallic sodium and be embedded in the mode of negative electrode tab come carry out mend sodium it is made
The sodium-ion battery 7 (number B2) obtained compares, and the coulombic efficiency for the first time of sodium-ion battery 1~5 (number is A1~A5) obtains
Raising is arrived, the utilization rate and whole energy density, cycle performance for improving sodium-ion battery active material are also mentioned
It rises.And with using metal simple-substance is mixed with sodium oxide molybdena, positive electrode is added collectively as additive, by the way of electrochemistry
The mode for discharging sodium ion therein carries out sodium-ion battery 8 (number B3) obtained by benefit sodium and compares, sodium-ion battery 1
The coulombic efficiency for the first time of~5 (number is A1~A5) is improved, improve sodium-ion battery active material utilization rate and
Whole energy density, cycle performance are also improved.
Sodium-ion battery cathode provided by the invention mends sodium method and sodium-ion battery, by that in an inert atmosphere, will consolidate
Liquid metal sodium after melting, is uniformly made an addition to the surface of negative electrode tab by the melting of state metallic sodium, and the metallic sodium after melting is in liquid
State can be embedded into the gap between the negative electrode material of negative electrode tab, so that metallic sodium is uniformly distributed in cathode.This
Invention does not finally have the inactive impurity such as metal oxide and remains in anode, do not need yet the configuration organic sodium solution of metal from
And cause to have organic substance residues in cathode, it is uniformly added by the liquid metal sodium obtained after directly melting solid metallic sodium fusion
It in the surface of negative electrode tab, simply and efficiently realizes and benefit sodium is carried out to sodium-ion battery, solving sodium-ion battery, coulomb is imitated for the first time
The low problem of rate improves the utilization rate and whole energy density of sodium-ion battery active material, to sodium-ion battery also without
Negative effect.
The above is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (10)
1. a kind of sodium-ion battery cathode mends sodium method, which is characterized in that include the following steps：
In an inert atmosphere, solid metallic sodium is melted under specified for temperature ranges, obtains liquid metal sodium；
The liquid metal sodium of specified amount is uniformly made an addition to the surface of negative electrode tab, so that the liquid metal sodium uniformly penetrates into
In gap between the negative electrode material of the negative electrode tab；
The dry negative electrode tab.
2. sodium-ion battery cathode according to claim 1 mends sodium method, which is characterized in that it is described in an inert atmosphere,
The step of melting under specified for temperature ranges, obtain liquid metal sodium solid metallic sodium include：
The inert gas of specified amount is inputted into melting tank, and opens vacuum heater and the melting tank is heated to assigned temperature
Range melts the solid metallic sodium, obtains liquid metal sodium.
3. sodium-ion battery cathode according to claim 1 mends sodium method, which is characterized in that by the liquid of specified amount
Metallic sodium uniformly makes an addition to the surface of negative electrode tab so that the liquid metal sodium uniformly penetrate into the negative electrode tab negative electrode material it
Between gap in step, including：
The liquid metal sodium is delivered to and is placed in the negative electrode tab in retractable volume system, by control the liquid metal sodium from
The speed that extrusion die squeezes out, amount and the position of the liquid metal sodium are added in control in the negative electrode tab, so that the liquid
State metallic sodium uniformly penetrates into the gap between the negative electrode material of the negative electrode tab.
4. sodium-ion battery cathode according to claim 1 mends sodium method, which is characterized in that the inert atmosphere used
Inert gas includes one or both of argon gas, helium.
5. sodium-ion battery cathode according to claim 1 mends sodium method, which is characterized in that the specified for temperature ranges packet
Include 98 DEG C to 200 DEG C.
6. sodium-ion battery cathode according to claim 1 mends sodium method, which is characterized in that the liquid of the specified amount
The range of state metallic sodium is the 1% to 25% of the negative electrode material total capacity of the negative electrode tab.
7. sodium-ion battery cathode according to claim 1 mends sodium method, which is characterized in that the cathode material of the negative electrode tab
Material includes one or more of hard carbon material, sulfide, oxide, metal simple-substance and alloy material.
8. a kind of sodium-ion battery, which is characterized in that including the use of the described in any item sodium-ion battery cathode of claim 1-7
Mend negative electrode tab made from sodium method.
9. sodium-ion battery according to claim 8, which is characterized in that it further include positive plate, the anode of the positive plate
Material include one of vanadium phosphate sodium, fluorophosphoric acid vanadium sodium, cobalt acid sodium, sodium manganate, nickel acid sodium and prussian blue material or
It is several.
10. sodium-ion battery according to claim 8, which is characterized in that the positive and negative anodes theoretical specific capacity proportion is 1:
1.03 to 1:1.2.
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| CN112768699A (en) * | 2021-01-11 | 2021-05-07 | 湖南立方新能源科技有限责任公司 | Sodium ion battery positive plate, preparation method thereof and sodium ion battery |
| CN113130896A (en) * | 2019-12-30 | 2021-07-16 | 珠海冠宇电池股份有限公司 | Positive electrode material for sodium ion battery and sodium ion battery comprising same |
| CN113793979A (en) * | 2021-08-18 | 2021-12-14 | 东莞塔菲尔新能源科技有限公司 | Secondary battery and power utilization device |
| CN114464953A (en) * | 2021-12-27 | 2022-05-10 | 国联汽车动力电池研究院有限责任公司 | Pre-sodium treatment method of diaphragm for sodium ion battery |
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