CN109478639A - A kind of benefit sodium method of sodium-ion battery and the pole piece and battery being prepared - Google Patents
A kind of benefit sodium method of sodium-ion battery and the pole piece and battery being prepared Download PDFInfo
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- CN109478639A CN109478639A CN201680087749.1A CN201680087749A CN109478639A CN 109478639 A CN109478639 A CN 109478639A CN 201680087749 A CN201680087749 A CN 201680087749A CN 109478639 A CN109478639 A CN 109478639A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
A kind of benefit sodium method of sodium-ion battery and the pole piece and battery being prepared, are related to secondary cell field.The benefit sodium method are as follows: prepare the first starting sheet of sodium-ion battery；Under an inert atmosphere, metallic sodium is prepared into molten state, then the metallic sodium of molten state is prepared in the surface of first starting sheet, form the metallic sodium layer for mending sodium for sodium-ion battery.The mode that sodium is mended in the melting can prevent from forming hole inside first starting sheet, and the amount for mending sodium can accurately be controlled by controlling the thickness of metallic sodium layer, and operation is simple.This method carries out benefit sodium using molten sodium, and operation temperature is lower, and production operation is safer, and energy consumption is lower.
Description
This application involves secondary cell fields, specifically, the pole piece and battery for being related to a kind of benefit sodium method of sodium-ion battery and being prepared.
Since lithium ion battery commercialization, the equipment power supply such as laptop computer, mobile phone market has been occupied rapidly with the advantages that high-energy density, high voltage, long-life, and is gradually applied to electric automobiles and extensive energy storage field in recent years.However, flourishing with electric vehicle industry and extensive energy storage industry, lithium resource price that is limited and being unevenly distributed can not have always been high any more, this may be a bottleneck problem for the extensive energy-storage battery for pursuing low cost, long-life.Therefore, there is an urgent need to develop a kind of novel long-lives, the energy storage device of low cost.
Reserves of the metallic sodium in the earth's crust are very abundant (accounting for about 2.74%), and are widely distributed, while sodium and lithium have many similar physicochemical properties.Compared with lithium ion battery, room temperature sodium-ion battery has apparent price advantage, therefore room temperature sodium-ion battery is expected to be applied to extensive energy storage field.
It is similar with lithium ion battery, for sodium-ion battery anode strip, during the initial charge of battery also due to the formation of solid electrolyte film (SEI film) and consume part sodium, therefore the loss of cathode material sodium is caused, to reduce the capacity and first charge discharge efficiency of battery.This is in common sodium-ion battery anode material --- and the performance on hard carbon is especially apparent.Currently, the coulombic efficiency for the first time of most of hard carbon material is equal less than 80%.
It is reduced to reduce battery battery capacity as caused by the formation of SEI film in initial charge, improves the energy density of battery, most effective way is to carry out pre- benefit sodium to pole piece.
In consideration of it, special propose the application.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of benefit sodium method of sodium-ion battery.
The second goal of the invention of the application is to propose a kind of sodium-ion battery pole piece.
The third goal of the invention of the application is to propose a kind of sodium-ion battery.
In order to complete the purpose of the application, the technical solution of use are as follows:
This application involves a kind of benefit sodium method of sodium-ion battery, the benefit sodium method is at least included the following steps:
(1) the first starting sheet of sodium-ion battery is prepared；
(2) under an inert atmosphere, metallic sodium is prepared into molten state, then the metallic sodium of molten state is prepared in the surface of the just starting sheet, form the metallic sodium layer for mending sodium for sodium-ion battery.
Preferably, in step (2), purity >=97% of the metallic sodium, preferably purity >=99% of metallic sodium.
Preferably, in step (2), the metallic sodium is prepared into the metallic sodium of molten state by heating, the temperature of heating is 98 DEG C~300 DEG C, preferably 103 DEG C~150 DEG C.
Preferably, in step (2), the metallic sodium layer that is prepared with a thickness of 0.5 μm~50 μm, preferably 1 μm~30 μm.
Preferably, in step (2), the metallic sodium of molten state is coated with or is sprayed on the surface of the just starting sheet.
Preferably, in step (2), the coating is extrusion coated or intaglio printing；The sprinkling is the surface that molten sodium is sprayed onto the just starting sheet using spray head, it is preferred that the fountain height of the molten sodium is 1.5 × 10-7g/mm2S~2.0 × 10-5g/mm2·s。
Preferably, it is coated or sprays after metallic sodium being melted in solvent, the boiling point of the solvent is lower than the melting temperature of metallic sodium, and does not react with sodium.
Preferably, the solvent is selected from at least one of aromatic solvent, esters solvent, ether solvent, at least one of more preferable toluene, dimethylbenzene, ethylene carbonate, propylene carbonate ester, diethyl carbonate, methyl ethyl carbonate, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether.
Preferably, in step (2), the consistency of thickness of the metallic sodium layer of formation.
Preferably, the metallic sodium layer be formed in the just starting sheet in the width direction on middle part, the two sides in the just starting sheet width direction form blank area, it is preferred that the width of the blank area
For 1mm~10mm.
Preferably, in step (2), the thickness for being formed by two side of the metallic sodium layer in the just starting sheet width direction is gradually become smaller.
Preferably, in step (1), it is described just starting sheet the preparation method comprises the following steps: by slurry coating on a current collector, be made after drying it is described just starting sheet, the water content of the just starting sheet is no more than 100ppm, and just starting sheet is placed in dry environment after drying；
Preferably, the dry environment is the humidity of environment less than 3%.
Preferably, in step (1), the just starting sheet is cathode just starting sheet or the first starting sheet of anode；Contain anode active material, binder and conductive agent in the initial anode pole piece；The anode active material is selected from carbon material, alloy material, excessively metal oxide, excessively at least one of plating metal sulfide, phosphorous-based materials or titanate material；Contain cathode active material, binder and conductive agent in the diaphragm of the initial cathode sheet；The cathode active material is selected from at least one of layer structure material, tunnel type oxide material, polyanionic material or Bu Lushi indigo plant.
Preferably, the alloy material is selected from the alloy material being made of at least two in Si, Ge, Sn, Pb and Sb；The metal oxide and the chemical formula for crossing plating metal sulfide crossed is M1xNy, wherein M1 is selected from at least one of Fe, Co, Ni, Cu, Mn, Sn, Mo, Sb, V, and N is selected from O or S；The phosphorous-based materials are selected from least one of red phosphorus, white phosphorus, black phosphorus；The titanate material is selected from Na2Ti3O7、Na2Ti6O13、Na4Ti5O12、Li4Ti5O12、NaTi2(PO4)3At least one；The chemical formula of layered structural material and the tunnel type oxide material is NaxM2O2, at least one of the M2 selected from Ti, V, Mn, Co, Ni, Fe, Cr, Cu；The polyanionic material is selected from NaFePO4、Na3V2(PO4)3、NaM3PO4F or Na3(VOx)2(PO4)2F3-2xAt least one of, M3 is selected from least one of V, Fe, Mn, Ni, 0≤x≤1；The chemical formula of the Bu Lushi blue material is NaxM4Fe(CN)6, M4 is selected from least one of Ni, Cu, Fe, Mn, Co, Zn.
The application further relates to the obtained sodium-ion battery pole piece using the preparation of above-mentioned benefit sodium method, and the sodium-ion battery pole piece is cathode sheet and/or anode pole piece.
The application further relates to a kind of sodium-ion battery, and including cathode sheet, anode pole piece, the isolation film and electrolyte being interval between the cathode sheet and the anode pole piece, the cathode sheet and/or anode pole piece are the sodium-ion battery pole piece of the application.
The technical solution of the application at least has following beneficial effect:
The benefit sodium method of the application not only can be improved the coulombic efficiency for the first time of active material in initial anode pole piece, to improve energy density, can also prevent from forming hole inside first starting sheet using in such a way that initial pole piece carries out melting benefit sodium.And the sodium-ion battery pole piece of the application can also get through the path of sodium ion in anode material by the sodium being added into rich sodium pole piece in advance, make the sodium ion in charge and discharge process be easier to carry out deintercalation in anode material, improve the capacity retention ratio of battery.
In the benefit sodium method of the application, the amount for mending sodium can accurately be controlled by controlling the thickness of metallic sodium layer, and operation is simple.The benefit sodium method of the application carries out benefit sodium using molten sodium, and operation temperature is lower, and production operation is safer, and energy consumption is lower.
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application rather than limitation scope of the present application.
For the first invention purpose of the application, the application proposes a kind of benefit sodium method of sodium-ion battery, it at least includes the following steps: preparing the first starting sheet of sodium-ion battery, under an inert atmosphere, metallic sodium is prepared into molten state, then the metallic sodium of molten state is prepared in the surface of the just starting sheet, form the metallic sodium layer for mending sodium for sodium-ion battery.The application mends sodium by melting to pole piece, its mesh first is that in order to improve the coulombic efficiency for the first time of active material in initial anode pole piece in the formation process of cell manufacturing process, reduce correspond to sodium ion in cathode material during first charge-discharge because material itself irreversible sodium ion capacity and formation SEI membrane process in cathode sodium ion loss, the coulombic efficiency for the first time of sodium-ion battery battery core is effectively improved, to improve the energy density of battery core.Its mesh second is that forming hole inside first starting sheet in order to prevent.Its third purpose is the path in order to get through sodium ion in anode material, makes the sodium ion in charge and discharge process be easier to carry out deintercalation in anode material, to improve the capacity retention ratio of battery.
For the mode of sodium is mended in vapor deposition or wet process, although vapour deposition process can deposit very thin sodium layer, the thickness of metallic sodium layer is more difficult to control during being somebody's turn to do, and whole process must be under vacuum conditions, metallic sodium evaporation is needed biggish energy consumption, higher cost simultaneously.It is that the solution containing sodium ion is dripped in pole piece that wet process, which mends sodium, then by chemistry or electrochemical process that the sodium in solution is embedding
Enter the method gone in pole piece.Although the method simple process, the process is longer, and production efficiency is lower.And the technical solution for mend by molten metal sodium sodium of the application, there is simple process, low in cost, efficiently and effectively advantage.
In this application, property or the convenience of description will be known as just starting sheet without mending the battery pole piece of sodium, the battery pole piece after mending sodium is become richness sodium pole piece.
A kind of improvement of sodium method is mended as the application, inert atmosphere is preferably argon gas or nitrogen or helium.Due to metallic sodium activity with higher itself, if encountering water or the carbon dioxide etc. in air, it is easy to happen the safety accidents such as explosion, it is therefore desirable to operate in an inert atmosphere, to guarantee production safety.
A kind of improvement of sodium method, purity >=97% of metallic sodium, preferably purity >=99% of metallic sodium are mended as the application.
Metallic sodium, is prepared into the metallic sodium of molten state by a kind of improvement that sodium method is mended as the application by heating, and the temperature of heating is 98 DEG C~300 DEG C, preferably 103 DEG C~150 DEG C.Metallic sodium preferably uses sodium block, and melting temperature cannot be too high, and otherwise the viscosity of molten sodium is too low, it is coated with or is sprayed onto after mending sodium pole piece and be easy flowing, the uniformity of benefit sodium is influenced, while excessively high temperature needs to consume more energy, is unfavorable for cost control；The melting temperature of sodium block can not be too low, and molten sodium can solidify in advance during being otherwise coated with or spraying, and is unfavorable for being coated with or spray.
A kind of improvement of sodium method is mended as the application, the benefit sodium capacity that the application mends the sodium amount and initial anode pole piece mended in sodium method is adapted.Wherein, after the meaning of " the benefit sodium capacity of initial anode pole piece " in the application refers to by way of mending sodium in advance, rich sodium anode pole piece improves increased pole piece capacity after head is imitated than first starting sheet.
As the application mend sodium method a kind of improvement, the metallic sodium layer being prepared with a thickness of 0.5 μm~50 μm, preferably 1 μm~30 μm.The application can be by accurately mending sodium to the control realization of the thickness of metallic sodium layer in preparation process.If the thickness of the metallic sodium layer of preparation is too thin, corresponding benefit sodium effect is not achieved；If the thickness of the metallic sodium layer of preparation is too thick, excessive sodium will lead to the precipitation of sodium dendrite, influence cell safety.
The metallic sodium of molten state is coated with or is sprayed on the surface of first starting sheet by a kind of improvement that sodium method is mended as the application.
A kind of improvement that sodium method is mended as the application is coated with as extrusion coated or intaglio printing, is sprayed for molten sodium to be sprayed onto the surface of first starting sheet using spray head.Wherein, extrusion coated or intaglio printing
Mode be comparative maturity in industrial production coating technique, in production efficiency, coating weight control, suffer from big advantage in terms of dimension control；In such a way that spray head is by molten sodium sprinkling, the molten sodium particle sprayed has certain kinetic energy, it is easier to adhere to pole piece.
A kind of improvement that sodium method is mended as the application, is coated or sprays after metallic sodium is melted in solvent.In a solvent by metallic sodium melting, it is sprayed onto pole piece after being uniformly dispersed, the sodium pearl being evenly distributed can be formed in pole piece, so that electrolyte be made to be easier to inside infiltration to pole piece, accelerated absorption of the pole piece to sodium layer is mended, improve and mend sodium efficiency.
In this scenario, it is desirable that the boiling point of solvent is lower than the melting temperature of metallic sodium, and does not react with sodium.Preferably, solvent can be selected from at least one of aromatic solvent, esters solvent or ether solvent, it is furthermore preferred that can be selected from least one of toluene, dimethylbenzene, ethylene carbonate, propylene carbonate ester, diethyl carbonate, methyl ethyl carbonate, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether.
A kind of improvement of sodium method is mended as the application, the fountain height of molten sodium is 1.5 × 10-7g/mm2S~2.0 × 10-5g/mm2·s.Under the conditions of the fountain height of the application setting, the operating time for completing the sodium supplementing amount of general requirements pole piece is 5~20s.If the molten sodium amount that molten sodium spray head sprays is too small, the overlong time for needing to spray influences production efficiency；If the molten sodium amount that molten sodium spray head sprays is excessive, the spraying time needed is too short, influences the feasibility of operation, while the excessive molten sodium kinetic energy sprayed that will lead to of molten sodium amount sprayed in the unit time is excessive, is easily destroyed pole piece.
A kind of improvement of sodium method, the consistency of thickness of the metallic sodium layer of formation are mended as the application.
Mend a kind of improvement of sodium method as the application, metallic sodium layer be formed in first starting sheet in the width direction on middle part, the two sides in the just starting sheet width direction form blank area, i.e., do not cover molten sodium layer on the blank area.
A kind of improvement of sodium method is mended as the application, the width of blank area is 1mm~10mm.If the width of blank area is excessive, it be easy to cause the amount for mending sodium insufficient；If the width of blank area is too small, it is easy precipitated sodium dendrite at the edge of pole piece, causes safety problem.
A kind of improvement of sodium method is mended as the application, the thickness for being formed by two side of the metallic sodium layer in first starting sheet width direction gradually becomes smaller.To which the effect of sodium is not mended in the avoidable part for not covering molten sodium layer.Preferably, when blank sector width is larger, the method is selected.
As the application mend sodium method a kind of improvement, first starting sheet the preparation method comprises the following steps: slurry is applied
It covers on a current collector, just starting sheet is made after drying, the water content of first starting sheet is no more than 100ppm.Because the activity of metallic sodium is higher, if the water content just in starting sheet is too high, can metallic sodium be reacted with water, cause the safety problems such as burning, explosion, influence the progress of production.
Just starting sheet is placed in dry environment after drying, and pole piece is avoided to reabsorb the moisture in environment.Preferably, dry environment is the humidity of environment less than 3%.
As the application mend sodium method a kind of improvement, first starting sheet can be drying after be cold-pressed before, cold pressing after, the pole piece after slitting or after soldering polar ear.
A kind of improvement of sodium method is mended as the application, first starting sheet is cathode just starting sheet or the first starting sheet of anode；Contain anode active material, binder and conductive agent in initial anode pole piece；Anode active material is selected from carbon material, alloy material, excessively metal oxide, excessively at least one of plating metal sulfide, phosphorous-based materials or titanate material；Contain cathode active material, binder and conductive agent in the diaphragm of initial cathode sheet；Cathode active material is at least one of layer structure material, tunnel type oxide material, polyanionic material or Bu Lushi indigo plant.
A kind of improvement of sodium method is mended as the application,
In anode active material:
Alloy material is selected from the alloy material being made of at least two in Si, Ge, Sn, Pb and Sb；
Crossing metal oxide and the chemical formula for crossing plating metal sulfide is M1xNy, wherein M1 is selected from at least one of Fe, Co, Ni, Cu, Mn, Sn, Mo, Sb, V, and N is selected from O or S；
Phosphorous-based materials are selected from least one of red phosphorus, white phosphorus, black phosphorus；
Titanate material is selected from Na2Ti3O7、Na2Ti6O13、Na4Ti5O12、Li4Ti5O12、NaTi2(PO4)3At least one；
In cathode active material:
The chemical formula of layer structure material and tunnel type oxide material is NaxM2O2, M2 is selected from least one of Ti, V, Mn, Co, Ni, Fe, Cr, Cu；
Polyanionic material is selected from NaFePO4、Na3V2(PO4)3、NaM3PO4F or Na3(VOx)2(PO4)2F3-2xAt least one of, M3 is selected from least one of V, Fe, Mn, Ni, 0≤x≤1；
The chemical formula of Bu Lushi blue material is NaxM4Fe(CN)6, M4 be selected from Ni, Cu, Fe, Mn,
At least one of Co, Zn.
For the second goal of the invention of the application, the application also proposes that the obtained sodium-ion battery richness sodium pole piece using the preparation of above-mentioned benefit sodium method, sodium ion richness sode cell pole piece are cathode richness sodium pole piece and/or anode richness sodium pole piece.
For the second goal of the invention of the application, application also proposes a kind of sodium-ion battery, including cathode sheet, anode pole piece, the isolation film and electrolyte being interval between cathode sheet and anode pole piece, wherein cathode sheet and/or anode pole piece are the sodium-ion battery richness sodium pole piece of the application.
Preparation example, embodiment and the experimental example that sodium method is mended according to the sodium-ion battery of the application will be illustrated next.
Preparation example
1, just starting sheet is prepared
Active material, binder, conductive agent are uniformly mixed with solvent according to mass ratio be made slurry (wherein, prepare anode just starting sheet when: binder is polyacrylic acid, and conductive agent is conductive carbon black, and solvent is deionized water；At the beginning of preparing cathode when starting sheet: binder is Kynoar, and conductive agent is conductive carbon black, and solvent is N-Methyl pyrrolidone), slurry is coated on the tow sides of collector and the coated weight in each face is 100mg/1540mm2；Then it dries, form diaphragm and the water content of diaphragm is made to be no more than 100ppm；The first starting sheet for being 160mm using obtained width after cold pressing, slitting, the corresponding tab of welding.
2, rich sodium pole piece is prepared
(1) rubbing method
Sodium block (purity) is melted, is melted at a certain temperature, the even spread certain thickness middle part upward along width in first starting sheet, and forms the blank area of one fixed width in first starting sheet two sides, richness sodium pole piece is made after temperature is cooled to room temperature.
(2) spray coating method
Sodium block (purity) is melted, is melted at a certain temperature, molten sodium is uniformly then sprayed on using certain fountain height by the first starting sheet middle part upward along width with spray head, spray time is 10 seconds；And the blank area of one fixed width is formed in first starting sheet two sides, richness sodium is made after temperature is cooled to room temperature
Pole piece.
3, sodium-ion battery is prepared:
Naked battery core is prepared in diaphragm and cathode sheet coiling by anode pole piece and after drying, then naked battery core is entered shell, fluid injection, and electrolyte is 1mol/L NaPF6Solvent is EC (ethylene carbonate): DEC (diethyl carbonate)=1:1 (volume ratio), it is stood in the environment of 25 DEG C later, liquid to be electrolysed is melted into after infiltrating, and (chemical conversion capacity finally obtains the sodium-ion battery of rich sodium battery core for ICCO), shaping, degassing process.
Embodiment
The rich sodium pole piece 1~17 prepared using rubbing method, it is specific as shown in table 1；Wherein the first starting sheet of rich sodium pole piece 1, rich sodium pole piece 8~12 is respectively adopted in first starting sheet 1~6.The rich sodium pole piece 18~33 prepared using spray coating method, it is specific as shown in table 2.
Table 1: the rich sodium pole piece being prepared using rubbing method
Note: the metallic sodium layer that thickness uniformly reduces is coated in the blank area that width is 5mm.
Table 2: the rich sodium pole piece being prepared using spray coating method
Note 1: the metallic sodium layer that thickness uniformly reduces is coated in the blank area that width is 5mm.
Note 2: sodium block is melted in toluene.
Wherein, in Tables 1 and 2: the gram volume of hard carbon is 200mAh/g, and the gram volume of Sb/C composite material is 610mAh/g, Na2Ti3O7Gram volume be 200mAh/g, Na2MnFe(CN)6Gram volume be 120mAh/g, Na2MnFe(CN)6Gram volume be 120mAh/g, Na3V2(PO4)3The phosphorus content of/C is 3.8%, gram volume 108mAh/g, Na0.90Cu0.22Fe0.30Mn0.48O2Gram volume be 100mAh/g.
Sodium-ion battery is prepared according to preceding method using the pole piece in Tables 1 and 2, specific as shown in table 3:
Table 3: the composition of pole piece in sodium-ion battery
| Number | Anode pole piece | Cathode sheet |
| Sodium-ion battery 1 | Rich sodium pole piece 1 | First starting sheet 4 |
| Sodium-ion battery 2 | Rich sodium pole piece 2 | First starting sheet 4 |
| Sodium-ion battery 3 | Rich sodium pole piece 3 | First starting sheet 4 |
| Sodium-ion battery 4 | Rich sodium pole piece 4 | First starting sheet 4 |
| Sodium-ion battery 5 | Rich sodium pole piece 5 | First starting sheet 4 |
| Sodium-ion battery 6 | Rich sodium pole piece 6 | First starting sheet 4 |
| Sodium-ion battery 7 | Rich sodium pole piece 7 | First starting sheet 4 |
| Sodium-ion battery 8 | Rich sodium pole piece 8 | First starting sheet 4 |
| Sodium-ion battery 9 | Rich sodium pole piece 9 | First starting sheet 4 |
| Sodium-ion battery 10 | First starting sheet 1 | Rich sodium pole piece 10 |
| Sodium-ion battery 11 | First starting sheet 1 | Rich sodium pole piece 11 |
| Sodium-ion battery 12 | First starting sheet 1 | Rich sodium pole piece 12 |
| Sodium-ion battery 13 | Rich sodium pole piece 13 | First starting sheet 4 |
| Sodium-ion battery 14 | Rich sodium pole piece 14 | First starting sheet 4 |
| Sodium-ion battery 15 | Rich sodium pole piece 15 | First starting sheet 4 |
| Sodium-ion battery 16 | Rich sodium pole piece 16 | First starting sheet 4 |
| Sodium-ion battery 17 | Rich sodium pole piece 17 | First starting sheet 4 |
| Sodium-ion battery 18 | Rich sodium pole piece 18 | First starting sheet 4 |
| Sodium-ion battery 19 | Rich sodium pole piece 19 | First starting sheet 4 |
| Sodium-ion battery 20 | Rich sodium pole piece 20 | First starting sheet 4 |
| Sodium-ion battery 21 | Rich sodium pole piece 21 | First starting sheet 4 |
| Sodium-ion battery 22 | Rich sodium pole piece 22 | First starting sheet 4 |
| Sodium-ion battery 23 | Rich sodium pole piece 23 | First starting sheet 4 |
| Sodium-ion battery 24 | Rich sodium pole piece 24 | First starting sheet 4 |
| Sodium-ion battery 25 | Rich sodium pole piece 25 | First starting sheet 4 |
| Sodium-ion battery 26 | Rich sodium pole piece 26 | First starting sheet 4 |
| Sodium-ion battery 27 | First starting sheet 1 | Rich sodium pole piece 27 |
| Sodium-ion battery 28 | First starting sheet 1 | Rich sodium pole piece 28 |
| Sodium-ion battery 29 | First starting sheet 1 | Rich sodium pole piece 29 |
| Sodium-ion battery 30 | Rich sodium pole piece 30 | First starting sheet 4 |
| Sodium-ion battery 31 | Rich sodium pole piece 31 | First starting sheet 4 |
| Sodium-ion battery 32 | Rich sodium pole piece 32 | First starting sheet 4 |
| Sodium-ion battery 33 | Rich sodium pole piece 33 | First starting sheet 4 |
| Compare sodium-ion battery 1 | First starting sheet 1 | First starting sheet 4 |
| Compare sodium-ion battery 2 | First starting sheet 2 | First starting sheet 4 |
| Compare sodium-ion battery 3 | First starting sheet 3 | First starting sheet 4 |
| Compare sodium-ion battery 4 | First starting sheet 1 | First starting sheet 5 |
| Compare sodium-ion battery 5 | First starting sheet 1 | First starting sheet 6 |
Experimental example
Method for testing performance:
Volume test: sodium-ion battery 1~33, comparison sodium-ion battery 1~5 are stood into 5min in 25 DEG C of environment；Then with the charging current constant-current charge of 0.1C to 4.0V, charging capacity AGCO is obtained；Stand 5min；Discharge capacity DO for the first time is obtained with the discharge current constant-current discharge of 0.1C to 2.0V again；It stands 5min and completes volume test later.
Calculate the formula of the coulombic efficiency for the first time of battery core are as follows: DO/ (ICCO+AGCO), acquired results are shown in Table 4.
Analyse sodium phenomenon: the benefit sodium effect for observing different sodium pieces or technique after above-mentioned volume test and the influence to pole piece section and appearance.
Table 4: the coulombic efficiency for the first time of battery
| Number | The coulombic efficiency for the first time of battery |
| Sodium-ion battery 1 | 100% |
| Sodium-ion battery 2 | 100% |
| Sodium-ion battery 3 | 99% |
| Sodium-ion battery 4 | 80% |
| Sodium-ion battery 5 | 100% |
| Sodium-ion battery 6 | 100% |
| Sodium-ion battery 7 | 99% |
| Sodium-ion battery 8 | 100% |
| Sodium-ion battery 9 | 100% |
| Sodium-ion battery 10 | 100% |
| Sodium-ion battery 11 | 100% |
| Sodium-ion battery 12 | 99% |
| Sodium-ion battery 13 | 100% |
| Sodium-ion battery 14 | 100% |
| Sodium-ion battery 15 | 100% |
| Sodium-ion battery 16 | 85% |
| Sodium-ion battery 17 | 100% |
| Sodium-ion battery 18 | 100% |
| Sodium-ion battery 19 | 100% |
| Sodium-ion battery 20 | 98% |
| Sodium-ion battery 21 | 95% |
| Sodium-ion battery 22 | 100% |
| Sodium-ion battery 23 | 100% |
| Sodium-ion battery 24 | 99% |
| Sodium-ion battery 25 | 100% |
| Sodium-ion battery 26 | 100% |
| Sodium-ion battery 27 | 100% |
| Sodium-ion battery 28 | 100% |
| Sodium-ion battery 29 | 100% |
| Sodium-ion battery 30 | 100% |
| Sodium-ion battery 31 | 100% |
| Sodium-ion battery 32 | 100% |
| Sodium-ion battery 33 | 100% |
| Compare sodium-ion battery 1 | 72% |
| Compare sodium-ion battery 2 | 83% |
| Compare sodium-ion battery 3 | 89% |
| Compare sodium-ion battery 4 | 74% |
| Compare sodium-ion battery 5 | 72% |
As can be seen from Table 4, the coulombic efficiency for the first time of sodium-ion battery 1~33 is superior to the coulombic efficiency for the first time of corresponding comparative example, therefore illustrates that the benefit sodium method using the sodium-ion battery of the application can effectively improve the coulombic efficiency for the first time of battery core.
Compare sodium-ion battery 1~3,18~20, it can be found that the width of blank area has a certain impact to sodium effect is mended.When blank sector width is smaller (such as sodium-ion battery 1,18), after battery core is dismantled
It can be found that pole piece edge has slight sodium dendrite to generate, safety problem is easily caused；When blank sector width is larger (such as sodium-ion battery 3,20), easily causes sodium supplementing amount deficiency and best benefit sodium effect is not achieved.
Compare sodium-ion battery 2,4,5, it can be found that the coating thickness of molten sodium is significant to sodium influential effect is mended.When thickness is too thin (such as sodium-ion battery 4), benefit sodium effect does not get a desired effect；When thickness is too thick (such as sodium-ion battery 5), then sodium excess is mended, it is apparent that mending sodium position has the generation of sodium dendrite after battery core is dismantled；When thickness is fallen between preferred thickness (such as sodium-ion battery 2), benefit sodium effect is the most significant, mends sodium position also without finding that apparent sodium dendrite generates after dismantling battery core.
Compare sodium-ion battery 2,6,7 and 19,24,25, it can be found that the melting temperature of molten sodium also has a certain impact to sodium effect is mended.When temperature is too low (such as sodium-ion battery 6,24), sodium just reaches molten condition, once uneven heating, part is easy condensation, influences Painting effect；When temperature is too high (such as sodium-ion battery 7,25), molten sodium viscosity living is smaller, is easy flowing after being coated with or being sprayed onto pole piece, influences the uniformity for mending sodium；When temperature falls in preferred range (such as sodium-ion battery 2,19), it is the most significant to mend sodium effect.
Compare sodium-ion battery 19,21,26, it can be found that the amount of the molten sodium of spray head sprinkling also has an impact to sodium effect is mended.When the amount of the molten sodium of spray head sprinkling is too small (such as sodium-ion battery 21), it be easy to cause sodium supplementing amount insufficient, optimal benefit sodium effect is not achieved；It when the amount of the molten sodium of spray head sprinkling is too big (such as sodium-ion battery 26), be easy to cause sodium supplementing amount excessive, dismantles after battery core it can be found that mending the generation that there is sodium dendrite in sodium position.
In conclusion the benefit sodium method of the sodium-ion battery of the application can carry out benefit sodium to sodium-ion battery effective and rapidly, the performance of sodium-ion battery is improved, simple production process is low in cost, easy to industrialized production.
Although the application is disclosed as above with preferred embodiment; it but is not for limiting claim; anyone skilled in the art are without departing from the concept of this application; several possible variations and modification can be made, therefore the protection scope of the application should be subject to the range that the claim of this application defined.
Claims (16)
- A kind of benefit sodium method of sodium-ion battery, which is characterized in that the benefit sodium method at least includes the following steps:(1) the first starting sheet of sodium-ion battery is prepared；(2) under an inert atmosphere, metallic sodium is prepared into molten state, then the metallic sodium of molten state is prepared in the surface of the just starting sheet, form the metallic sodium layer for mending sodium for sodium-ion battery.
- Benefit sodium method according to claim 1, which is characterized in that in step (2), purity >=97% of the metallic sodium, preferably purity >=99% of metallic sodium.
- Benefit sodium method according to claim 1, which is characterized in that in step (2), the metallic sodium is prepared into the metallic sodium of molten state by heating, the temperature of heating is 98 DEG C~300 DEG C, preferably 103 DEG C~150 DEG C.
- Benefit sodium method according to claim 1, which is characterized in that in step (2), the metallic sodium layer that is prepared with a thickness of 0.5 μm~50 μm, preferably 1 μm~30 μm.
- Benefit sodium method according to claim 1, which is characterized in that in step (2), the metallic sodium of molten state is coated with or is sprayed on the surface of the just starting sheet.
- Benefit sodium method according to claim 5, which is characterized in that in step (2), the coating is extrusion coated or intaglio printing；The sprinkling is the surface that molten sodium is sprayed onto the just starting sheet using spray head, it is preferred that the fountain height of the molten sodium is 1.5 × 10-7g/mm2S~2.0 × 10-5g/mm2·s。
- Benefit sodium method according to claim 5, which is characterized in that be coated or spray after metallic sodium is melted in solvent, the boiling point of the solvent is lower than the melting temperature of metallic sodium, and does not react with sodium.
- Benefit sodium method according to claim 7, it is characterized in that, the solvent is selected from at least one of aromatic solvent, esters solvent, ether solvent, at least one of more preferable toluene, dimethylbenzene, ethylene carbonate, propylene carbonate ester, diethyl carbonate, methyl ethyl carbonate, glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether.
- Benefit sodium method according to claim 1, which is characterized in that in step (2), the consistency of thickness of the metallic sodium layer of formation.
- Benefit sodium method according to claim 9, it is characterized in that, the metallic sodium layer be formed in the just starting sheet in the width direction on middle part, the two sides in the just starting sheet width direction form blank area, preferably, the width of the blank area is 1mm~10mm.
- Benefit sodium method according to claim 1, which is characterized in that in step (2), the thickness for being formed by two side of the metallic sodium layer in the just starting sheet width direction is gradually become smaller.
- Benefit sodium method according to claim 1, it is characterized in that, in step (1), it is described just starting sheet the preparation method comprises the following steps: by slurry coating on a current collector, the just starting sheet is made after drying, the water content of the just starting sheet is no more than 100ppm, and just starting sheet is placed in dry environment after drying；Preferably, the dry environment is the humidity of environment less than 3%.
- Benefit sodium method according to claim 1, which is characterized in that in step (1), the just starting sheet is cathode just starting sheet or the first starting sheet of anode；Contain anode active material, binder and conductive agent in the initial anode pole piece；The anode active material is selected from carbon material, alloy material, excessively metal oxide, excessively at least one of plating metal sulfide, phosphorous-based materials or titanate material；Contain cathode active material, binder and conductive agent in the diaphragm of the initial cathode sheet；The cathode active material is selected from at least one of layer structure material, tunnel type oxide material, polyanionic material or Bu Lushi indigo plant.
- Benefit sodium method according to claim 13, which is characterized in that the alloy material is selected from the alloy material being made of at least two in Si, Ge, Sn, Pb and Sb；The metal oxide and the chemical formula for crossing plating metal sulfide crossed is M1xNy, wherein M1 is selected from at least one of Fe, Co, Ni, Cu, Mn, Sn, Mo, Sb, V, and N is selected from O or S；The phosphorous-based materials are selected from least one of red phosphorus, white phosphorus, black phosphorus；The titanate material is selected from Na2Ti3O7、Na2Ti6O13、Na4Ti5O12、Li4Ti5O12、NaTi2(PO4)3At least one；The chemical formula of layered structural material and the tunnel type oxide material is NaxM2O2, at least one of the M2 selected from Ti, V, Mn, Co, Ni, Fe, Cr, Cu；The polyanionic material is selected from NaFePO4、Na3V2(PO4)3、NaM3PO4F or Na3(VOx)2(PO4)2F3-2xAt least one of, M3 is selected from least one of V, Fe, Mn, Ni, 0≤x≤1；The chemical formula of the Bu Lushi blue material is NaxM4Fe(CN)6, M4 is selected from least one of Ni, Cu, Fe, Mn, Co, Zn.
- A kind of obtained sodium-ion battery pole piece of the benefit sodium method preparation as described in claim 1~14, the sodium-ion battery pole piece is cathode sheet and/or anode pole piece.
- A kind of sodium-ion battery, including cathode sheet, anode pole piece, the isolation film and electrolyte being interval between the cathode sheet and the anode pole piece, it is characterized in that, the cathode sheet and/or anode pole piece are sodium-ion battery pole piece described in claim 15.
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| PCT/CN2016/090328 WO2018014164A1 (en) | 2016-07-18 | 2016-07-18 | Method for supplementing sodium ion battery with sodium and electrode sheet and battery obtained by preparation |
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Cited By (4)
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| CN109888179A (en) * | 2019-03-29 | 2019-06-14 | 华中科技大学 | A kind of high-performance sodium-ion battery titanium-based cathode, sodium-ion battery and preparation method |
| CN114899410A (en) * | 2022-06-02 | 2022-08-12 | 江苏天合储能有限公司 | Current collector and manufacturing method thereof |
| CN115472784A (en) * | 2022-08-16 | 2022-12-13 | 北京航空航天大学 | Na 3 Ti 2 (PO 4 ) 3 Preparation method of positive electrode and application of positive electrode in sodium ion battery |
| WO2023133805A1 (en) * | 2022-01-14 | 2023-07-20 | 宁德时代新能源科技股份有限公司 | Positive electrode composite material for lithium ion secondary battery, positive electrode and battery |
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| CN108878780A (en) * | 2018-06-08 | 2018-11-23 | 欣旺达电子股份有限公司 | Sodium-ion battery cathode mends sodium method and sodium-ion battery |
| CN113130896B (en) * | 2019-12-30 | 2022-11-22 | 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 |
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