CN109565037A - Sodium-ion battery pole piece, preparation method and the sodium-ion battery containing the pole piece - Google Patents
Sodium-ion battery pole piece, preparation method and the sodium-ion battery containing the pole piece Download PDFInfo
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- CN109565037A CN109565037A CN201680087757.6A CN201680087757A CN109565037A CN 109565037 A CN109565037 A CN 109565037A CN 201680087757 A CN201680087757 A CN 201680087757A CN 109565037 A CN109565037 A CN 109565037A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A kind of sodium-ion battery pole piece, preparation method and the sodium-ion battery containing the pole piece are provided.Sodium-ion battery pole piece includes sodium piece, collector and the diaphragm being attached on collector, and collector and diaphragm form just starting sheet, and sodium piece is set on just starting sheet.The coulombic efficiency for the first time of battery can be improved in electrode plates, reduces the loss of the sodium ion in cathode material during first charge-discharge, while the sodium ion in charge and discharge process being made to be easier the deintercalation in anode material, improves the capacity retention ratio of battery.Preparation method is easily operated, with short production cycle, efficient, it can be achieved that quantitatively mending sodium.
Description
This application involves secondary cell fields, specifically, are related to a kind of sodium-ion battery pole piece, preparation method and the sodium-ion battery containing the pole piece.
Energy shortage and environmental problem propose new demand to the exploitation and construction of large-scale energy storage device.As the lithium ion battery of advanced rechargeable secondary cell, in terms of being widely used in consumer electronics product and energy automobile.However, the problems such as lithium ion battery still suffers from security risk, and the expensive and global lithium resource of cost of material is short.And these problems largely constrain the development base application of lithium ion battery, especially in terms of extensive energy storage.Therefore development resource is enriched, low-cost Xi'an is into battery system, is the inevitable outlet for solving the following large-scale energy storage system application.Sodium element is of the same clan with lithium, and electrochemical properties are similar, and electrode TV is also relatively.And resource of the sodium element in the whole world is very rich, is 2.64%, significantly larger than the 0.006% of elemental lithium, and cost is relatively low for refinement.If developing excellent working performance, low-cost sodium-ion battery, then it will possess has bigger competitive advantage than lithium ion battery battery in terms of extensive energy storage.
However, sodium ion radius ratio lithium ion radius is big, sodium ion is embedded in and deviates from more difficult in crystal structure materials of the same race than lithium ion in positive anode material, part sodium ion is caused to stay in anode and can not be successfully abjection in charge and discharge process, simultaneously during first charge-discharge, SEI film is formed in anode, sodium ion is further consumed, causes the first charge-discharge coulombic efficiency of sodium-ion battery lower.By taking carbon material as an example, graphite type material has preferable application in lithium ion battery, and charge-discharge property can reach 94~95% or so.And insertion and abjection that same type of material sodium ion can not be successfully, it is difficult to apply in sodium-ion battery.And hard carbon material can make sodium ion smoothly be embedded in abjection, however, its efficiency for charge-discharge is lower, be extremely difficult to 90%.Therefore the coulombic efficiency for needing to find a kind of suitable method raising sodium-ion battery, improves its chemical property.
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 sodium-ion battery pole piece.
The second goal of the invention of the application is to propose the preparation method of the sodium-ion battery pole piece.
The third goal of the invention of the application is to propose the sodium-ion battery containing the pole piece.
In order to complete the purpose of the application, the technical solution of use are as follows:
This application involves a kind of sodium-ion battery pole piece, the sodium-ion battery pole piece includes sodium piece, collector and the diaphragm being attached on the collector, and the collector and the diaphragm form just starting sheet, and the sodium piece is set on the just starting sheet.
Preferably, the sodium piece is incorporated on the just starting sheet through cold pressing.
Preferably, the sodium piece with a thickness of 1 μm~500 μm, preferably 5 μm~100 μm.
Preferably, the width of the sodium piece is a, and the width of the just starting sheet is b, a≤b；Preferably, 80%b≤a≤b；It is furthermore preferred that 80%b≤a≤98%b.
Preferably, the sodium piece is set to the middle part of the initial sodium piece.
Preferably, the collector is selected from one of aluminium foil, copper foil, stainless steel foil, porous aluminium foil, porous copper foil, porous stainless steel foil.
Preferably, the just starting sheet includes initial anode pole piece and initial cathode sheet.
Preferably, the benefit sodium capacity of the amount containing sodium of the sodium piece and the initial anode pole piece is adapted.
Preferably, anode active material, binder and conductive agent are contained in the diaphragm of 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)3
At 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 preparation method of the sodium-ion battery pole piece, at least includes the following steps: preparing just starting sheet, in dry environment, the sodium piece is covered in the membrane surface of the just starting sheet to get the sodium-ion battery pole piece.
Preferably, it is cold-pressed after the sodium piece being covered in the just membrane surface of starting sheet.
Preferably, the pressure of the cold pressing is 0.01~1.5Mpa；Preferably, pressure is 0.2~1.0Mpa.
Preferably, the just starting sheet the preparation method comprises the following steps: active material, conductive agent, binder and stirring solvent are uniformly obtained slurry, on a current collector by slurry coating, by drying, just starting sheet is obtained after cold pressing, wherein the slurry coated on a current collector becomes diaphragm after drying cold pressing.
The application further relates to a kind of sodium-ion battery, including anode pole piece, cathode pole piece, the isolation film and electrolyte being interval between the anode pole piece and the cathode pole piece, it is characterized in that, the anode pole piece and/or cathode 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 coulombic efficiency for the first time of active material in pole piece can be improved in the sodium-ion battery pole piece of the application, reduce the loss of cathode sodium ion during first charge-discharge, the sodium that the sodium-ion battery pole piece of the application can be also added into rich sodium pole piece by way of mending sodium in advance gets through the path of sodium ion in anode material, make the sodium ion in charge and discharge process be easier to carry out deintercalation in anode material, improves the capacity retention ratio of battery.
The preparation method of the sodium-ion battery pole piece of the application be not only easy to operation, it is with short production cycle, efficient, and also can reach it is quantitative control mend sodium effect.
Fig. 1 is the capacity retention ratio comparison diagram of 1 sodium-ion battery of embodiment 1 and comparative example.
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 that a kind of sodium-ion battery pole piece, sodium-ion battery pole piece include collector, the diaphragm being attached on collector and sodium piece, and collector and diaphragm form just starting sheet, and sodium piece is set on just starting sheet.It is to carry out pre- benefit sodium to anode that sodium piece is arranged in the application sodium-ion battery pole piece, one of its mesh is coulombic efficiency for the first time in order to improve 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, its second purpose is the path in order to get through sodium ion in anode material, the sodium ion in charge and discharge process is set to be easier to carry out deintercalation in anode material, to improve the capacity retention ratio of battery.
The sodium source that sodium is mended in the application uses sodium piece in homogeneous thickness, uniformly mends sodium for anode to realize.Sodium piece surface is prepared with passivation layer in process of production in the application, and metamorphic reaction will not occur for (humidity in air is less than 5%) in dry environment, and passivation layer can be oxidation film or nitride film.
As a kind of improvement of the application sodium-ion battery pole piece, sodium piece is incorporated on just starting sheet through cold pressing.That is, the application is to be combined sodium piece with diaphragm in such a way that sodium piece is by cold pressing.By cold pressing, sodium piece is incorporated on just starting sheet, increases the contact of sodium piece and diaphragm active material, convenient for the progress of the processes such as subsequent naked battery core battery core.Method is crossed using electrolysis method, steaming positive anode material is carried out to mix sodium processing in advance, although the first charge-discharge efficiency of sodium-ion battery also can be improved, but it steams the method for crossing to need to be operated at high temperature, may the high molecular materials such as binder in pole piece be caused with adverse effect, and electrolysis method may introduce other impurity because of electrolyte, on battery performance, there may be influences, and its low efficiency, the production cycle is long, requires production equipment high, operating difficulties is unfavorable for being mass produced.And the application using cold pressing by the way of then be not only easy to operation, it is with short production cycle, efficient, and also can reach it is quantitative control mend sodium effect.
As a kind of improvement of the application sodium-ion battery pole piece, first starting sheet includes initial anode pole piece or initial cathode sheet.
The sodium-ion battery pole piece of the application can be anode pole piece or cathode sheet.Cathode sheet containing sodium piece is known as cathode richness sodium pole piece in this application by property or the convenience of description, and the anode pole piece containing sodium piece is known as anode richness sodium pole piece.Anode richness sodium pole piece can increase contact of the sodium piece with anode active material, and anode active material is made quickly to absorb the sodium in sodium piece, achieve the effect that pre- benefit sodium.Using cathode richness sodium pole piece, sodium ion quickly can reach anode from cathode by diaphragm in charge and discharge process, and stable SEI film is formed in anode surface, form the section of preferable anode.Therefore, the pre- benefit sodium effect to sodium-ion battery may be implemented in anode richness sodium pole piece or cathode richness sodium pole piece.
As a kind of improvement of the application sodium-ion battery pole piece, the benefit sodium capacity of the amount containing sodium of sodium piece and initial anode pole piece is adapted.The application can accurately mend sodium to anode by the amount containing sodium in sodium piece.
Wherein, the meaning of " amount containing sodium " in the application refers to the capacity of sodium in the sodium piece for mending sodium.
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.
The meaning of " adaptable " includes the case where that the amount containing sodium of sodium piece and the benefit sodium capacity of starting sheet at the beginning of anode are completely the same in the application, also includes the case where that the amount containing sodium of sodium piece is more than or less than the benefit sodium capacity of first starting sheet.It is full benefit sodium when the amount containing sodium of sodium piece is equal with for the benefit sodium capacity of starting sheet at the beginning of anode, is overfill sodium when the amount containing sodium of sodium piece is greater than the benefit sodium capacity of starting sheet at the beginning of anode, is underfill sodium when the amount containing sodium of sodium piece is less than the benefit sodium capacity of starting sheet at the beginning of anode.
As a kind of improvement of the application sodium-ion battery pole piece, sodium piece with a thickness of 1 μm~500 μm, preferably 5 μm~100 μm.When the timing of area one of sodium piece, i.e., by controlling the benefit sodium capacity to initial anode pole piece to sodium piece thickness.
As a kind of improvement of the application sodium-ion battery pole piece, the width of sodium piece is a, and the width of first starting sheet is b, a≤b.Sodium piece width is less than or equal to the width of first starting sheet, when sodium piece width is greater than pole piece width, in fact it could happen that metallic sodium passes through isolation film and another pole active contacts, so that short circuit be caused to cause danger.Since sodium piece has certain ductility, preferred sodium piece width is less than the width of first starting sheet.
As a kind of improvement of the application sodium-ion battery pole piece, the relationship of sodium piece width and first starting sheet width are as follows: 80%b≤a≤b；When sodium piece width is less than the 80% of pole piece width, pole piece can not be spread completely in a short time, influenced pole piece edge and mended sodium effect, cause benefit sodium uneven.
As a kind of improvement of the application sodium-ion battery pole piece, sodium piece width and first starting sheet width
Relationship are as follows: 80%b≤a≤98%b；It in view of pole piece is after lamination or winding are prepared into battery core, is under pressure in the techniques such as the top side seal of subsequent handling or molding, the material is soft for sodium piece, has certain deformation and extends.If sodium piece width and the width gap of first starting sheet are too small, local micro-short circuit is likely to occur before formation process in process, reduces the battery core survival rate in preparation process, therefore further preferably a≤98%b.
As a kind of improvement of the application sodium-ion battery pole piece, the relationship of sodium piece width and first starting sheet width are as follows: 90%b≤a≤98%b.
As a kind of improvement of the application sodium-ion battery pole piece, sodium piece is set to the middle part of initial sodium piece, i.e., the two sides in first starting sheet width direction form blank area.
As a kind of improvement of the application sodium-ion battery pole piece, collector is selected from one of aluminium foil, copper foil, stainless steel foil, porous aluminium foil, porous copper foil, porous stainless steel foil.
As a kind of improvement of the application sodium-ion battery pole piece, contain anode active material, binder and conductive agent in the diaphragm of 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 selected from at least one of layer structure material, tunnel type oxide material, polyanionic material or Bu Lushi indigo plant.
As a kind of improvement of the application sodium-ion battery pole piece,
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；
The chemical formula of layer structure material and tunnel type oxide material is NaxM2O2, at least one of the M2 selected from 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 in V, Fe, Mn, Ni at least one
Kind, 0≤x≤1；The chemical formula of Bu Lushi blue material is NaxM4Fe(CN)6, M4 is selected from least one of Ni, Cu, Fe, Mn, Co, Zn.
For the second goal of the invention of the application, the application proposes the preparation method of above-mentioned sodium-ion battery pole piece, at least includes the following steps:
It prepares just starting sheet and sodium piece is covered in the membrane surface of first starting sheet to get sodium-ion battery pole piece in dry environment.
As a kind of improvement of the application preparation method, sodium piece is covered in the membrane surface of first starting sheet, using cold pressing process；The contact that sodium piece with diaphragm active material can be increased improves it because two kinds of solid phases cause ion transport slower, to speed its infiltration rate to sodium piece.
In this application, dry environment refers to the humidity in environmental air less than 5%.
As a kind of improvement of the application preparation method, pressure when cold pressing is 0.01~1.5Mpa；Preferably, pressure is 0.2~1.0Mpa.In cold pressure procedure, if pressure is excessive, just starting sheet deformation may cause, influence the preparation process of sodium-ion battery, pressure is too small, then is unable to reach and increases its purpose for being bonded effect, so cold pressing pressure should be controlled in 1.5Mpa once to guarantee the appearance formedness of pole piece.Preferably, pressure control guarantees that it is cold-pressed effect in 0.2~1.0Mpa.
A kind of improvement as the application preparation method, first starting sheet the preparation method comprises the following steps: active material, conductive agent, binder and stirring solvent are uniformly obtained slurry, on a current collector by slurry coating, by drying, just starting sheet is obtained after cold pressing, wherein the slurry coated on a current collector becomes diaphragm after drying cold pressing.
As a kind of improvement of the application preparation method, the time for being prepared as first starting sheet to be covered with the rich sodium pole piece of sodium piece is 1~10 minute.
For the second goal of the invention of the application, the application proposes a kind of sodium-ion battery, including anode pole piece, cathode pole piece, the isolation film and electrolyte being interval between anode pole piece and cathode pole piece, wherein anode pole piece and/or cathode pole piece are the sodium-ion battery pole piece of the application.
Preferably, anode pole piece or cathode pole piece are the sodium-ion battery pole piece of the application.
It the steps include: starting sheet at the beginning of the anode pole piece of the application, cathode and isolation film naked battery core is made by winding or lamination, or starting sheet, the cathode pole piece of the application and isolation film at the beginning of anode passed through
Naked battery core is made in winding or lamination；Then naked battery core is fitted into battery packages shell and carries out top side seal, inject electrolyte later, using standing, shaping, sodium-ion battery is made in the techniques such as chemical conversion.
In order to be more clear goal of the invention of the invention, technical solution and its advantageous effects, following embodiment and comparative example, the present invention will be described in further detail.It should be understood that embodiment described in this specification is merely to the explanation present invention, is not intended to limit the present invention.Raw material use herein is marketable material.
Preparation example
(1) anode pole piece
1, it prepares initial anode pole piece: anode active material, binder, conductive agent being uniformly mixed according to the ratio that mass ratio is 88:10:2 with solvent and are prepared into slurry；Wherein, binder PAA, conductive agent are conductive black, and solvent is water.Slurry is coated on copper current collector, coating weight 100mg/1540mm2, it is b by the width of pole piece that pole piece obtains sodium-ion battery anode pole piece after drying, cold pressing, slitting；
2, it prepares rich sodium anode pole piece: in dry environment, certain thickness, the sodium piece that width is a being covered on the surface (the case where i.e. cold pressing pressure is zero) of first starting sheet, rich sodium anode pole piece is obtained；Or the first starting sheet for being covered with sodium piece is added certain pressure, obtain rich sodium anode pole piece by cold pressing.First starting sheet is prepared as the time of rich sodium pole piece by record simultaneously.
(2) cathode sheet
1, it prepares initial cathode sheet: cathode active material, binder, conductive agent being uniformly mixed according to the ratio that mass ratio is 88:10:2 with solvent and are prepared into slurry, wherein, binder is PVDF, and conductive agent is conductive black, and solvent is N-Methyl pyrrolidone (NMP)；Slurry is coated on aluminium collector, coating weight 0.33g/1540mm2, pole piece obtains sodium-ion battery anode pole piece after drying, cold pressing, slitting, and it is b that pole piece, which is cut into width,；
2, it prepares rich sodium cathode pole piece: in dry environment, 10 μm of certain thickness, the sodium piece that width is a being covered on to the surface (the case where i.e. cold pressing pressure is zero) of first starting sheet, obtain rich sodium anode pole piece；Or the first starting sheet for being covered with sodium piece is added certain pressure, obtain rich sodium anode pole piece by cold pressing.First starting sheet is prepared as the time of rich sodium pole piece by record simultaneously.
(3) preparation of sodium-ion battery
Naked battery core is made by lamination in the cathode sheet, anode pole piece and isolation film of sodium-ion battery；Then after battery core being fitted into laminated aluminum film, by top side seal technique, electrolyte is injected later, and using standing, shaping, sodium-ion battery is made in the techniques such as chemical conversion.
Embodiment
It is prepared as described above method and prepares rich sodium pole piece 1~16, first starting sheet 1~6 respectively, design parameter is as shown in table 1:
Table 1:
The rich sodium pole piece of comparative example 1 uses evaporation coating method, concrete technology condition are as follows: using vapor deposition by metallic sodium layer vapor deposition to anode initial film on piece, it is 150mm by baffle controls width that thickness of coating, which is 10 μm, i.e. coating is identical as above embodiments 1.The time of equivalent Na layers of vapor deposition is 30min, and the front and back pumpdown time is 150min, and it is about 180min that the end time is prepared from first starting sheet to rich sodium pole piece.
The rich sodium pole piece of comparative example 2 uses electro-plating method, concrete technology condition are as follows: metallic sodium layer is electroplated by initial film on piece using electroplating device, electrolyte is sodium hexafluoro phosphate, and thickness of coating is 10 μm, it is 150mm by baffle controls width, i.e. coating is identical as above embodiments 1.The time of equivalent Na layers of plating is about 20min, and front and back reaches electrolytic condition time about 10min, and it is about 30min that the end time is prepared from first starting sheet to rich sodium pole piece.
The design parameter of comparative example 1 and 2 is as shown in table 2:
Table 2:
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 6 |
| Sodium-ion battery 2 | Rich sodium pole piece 2 | First starting sheet 6 |
| Sodium-ion battery 3 | Rich sodium pole piece 3 | First starting sheet 6 |
| Sodium-ion battery 4 | Rich sodium pole piece 4 | First starting sheet 6 |
| Sodium-ion battery 5 | Rich sodium pole piece 5 | First starting sheet 6 |
| Sodium-ion battery 6 | Rich sodium pole piece 6 | First starting sheet 6 |
| Sodium-ion battery 7 | Rich sodium pole piece 7 | First starting sheet 6 |
| Sodium-ion battery 8 | Rich sodium pole piece 8 | First starting sheet 6 |
| Sodium-ion battery 9 | Rich sodium pole piece 9 | First starting sheet 6 |
| Sodium-ion battery 10 | Rich sodium pole piece 10 | First starting sheet 6 |
| Sodium-ion battery 11 | Rich sodium pole piece 11 | First starting sheet 6 |
| Sodium-ion battery 12 | Rich sodium pole piece 12 | First starting sheet 6 |
| Sodium-ion battery 13 | Rich sodium pole piece 13 | First starting sheet 6 |
| Sodium-ion battery 14 | First starting sheet 1 | Rich sodium pole piece 14 |
| Sodium-ion battery 15 | First starting sheet 1 | Rich sodium pole piece 15 |
| Sodium-ion battery 16 | First starting sheet 1 | Rich sodium pole piece 16 |
| Compare sodium-ion battery 1 | First starting sheet 1 | First starting sheet 6 |
| Compare sodium-ion battery 2 | First starting sheet 2 | First starting sheet 6 |
| Compare sodium-ion battery 3 | First starting sheet 3 | First starting sheet 6 |
| Compare sodium-ion battery 4 | First starting sheet 4 | First starting sheet 6 |
| Compare sodium-ion battery 5 | First starting sheet 1 | First starting sheet 5 |
| Compare sodium-ion battery 6 | Rich sodium pole piece D1 | First starting sheet 6 |
| Compare sodium-ion battery 7 | Rich sodium pole piece D2 | First starting sheet 6 |
Experimental example
Performance test:
Coulombic efficiency for the first time:Sodium-ion battery sodium-ion battery 1~16 and the sodium-ion battery for comparing sodium-ion battery 1~7 are subjected to constant current charge-discharge test at 25 DEG C, its charge and discharge step are as follows: with 0.7C multiplying power constant-current charge to voltage be 4.0V, it is later 0.05C with 4.0V constant-voltage charge to electric current, sodium-ion battery reaches fully charged state at this time, stands 5min later；It is 1.5V with 0.5C multiplying power constant-current discharge to voltage, then stands 5min；For a cycle charge discharge electric process.Time discharge capacity and initial charge capacity are measured in the method.
Discharge capacity/initial charge capacity × 100% of coulombic efficiency=for the first time for the first time.
After tested, sodium-ion battery 1~16 is calculated and compares the sodium of sodium-ion battery 1~7
The coulombic efficiency for the first time of ion battery is as shown in table 4.
Analyse sodium phenomenon: it carries out the sample of sodium-ion battery 1~16 and comparison sodium-ion battery 1~7 to charge to 4.0V under the multiplying power of 0.7C, it is later 0.05C in 4.0V constant-voltage charge to electric current, and battery core is dismantled under fully charged state, the benefit sodium effect for observing different sodium pieces or technique and the influence to pole piece section and appearance.
Cycle performance: the sodium-ion battery of sodium-ion battery 1 and comparison sodium-ion battery 1 is subjected to constant current charge-discharge test at 25 DEG C, its charge and discharge step are as follows: with 0.7C multiplying power constant-current charge to voltage be 4.0V, it is later 0.05C with 4.0V constant-voltage charge to electric current, sodium-ion battery reaches fully charged state at this time, stands 5min later；It is 1.5V with 0.5C multiplying power constant-current discharge to voltage, then stands 5min；For a cycle charge discharge electric process.50 charge and discharge cycles are carried out, the capacity retention ratio of each circulation is calculated.
The capacity retention ratio of sodium-ion battery 1 and comparison 1 sodium-ion battery of sodium-ion battery is as shown in Figure 1.
Table 4:
| Coulombic efficiency | |
| Sodium-ion battery 1 | 90.6% |
| Sodium-ion battery 2 | 92.3% |
| Sodium-ion battery 3 | 93.1% |
| Sodium-ion battery 4 | 91.0% |
| Sodium-ion battery 5 | 87.6% |
| Sodium-ion battery 6 | 89.9% |
| Sodium-ion battery 7 | 90.3% |
| Sodium-ion battery 8 | 86.7% |
| Sodium-ion battery 9 | 88.2% |
| Sodium-ion battery 10 | 92.1% |
| Sodium-ion battery 11 | 85.7% |
| Sodium-ion battery 12 | 86.9% |
| Sodium-ion battery 13 | 82.3% |
| Sodium-ion battery 14 | 90.3% |
| Sodium-ion battery 15 | 88.5% |
| Sodium-ion battery 16 | 91.0% |
| Compare sodium-ion battery 1 | 80.2% |
| Compare sodium-ion battery 2 | 70.1% |
| Compare sodium-ion battery 3 | 75.3% |
| Compare sodium-ion battery 4 | 62.7% |
| Compare sodium-ion battery 5 | 81.2% |
| Compare sodium-ion battery 6 | 91.0% |
| Compare sodium-ion battery 7 | 90.8% |
(1) compare sodium-ion battery 1~16 and compare the coulombic efficiency for the first time of sodium-ion battery 1~5, it can be found that: it is all significantly improved than the corresponding coulombic efficiency for the first time for comparing the first starting sheet in sodium-ion battery using the first effect of the sodium-ion battery of rich sodium pole piece, illustrate that the rich sodium pole piece by sodium piece embedding sodium pre- to pole piece can effectively improve the coulombic efficiency for the first time of sodium-ion battery, improves its chemical property.
(2) compare sodium-ion battery 1~5, active material is identical, because the thickness of sodium piece is not identical as width and cause for the first time coulombic efficiency be slightly different.Rear pole piece is completely filled in observation, it is found that the pole piece interface homogeneity of sodium-ion battery 1~3 is good, and without apparent analysis sodium phenomenon.
It is remaining that there is part sodium at the pole piece edge of sodium-ion battery 4, and remaining a small amount of sodium some areas have exceeded the width of initial diaphragm.This is because after initial diaphragm covers sodium piece, there is the process of cold pressing, and in the top side seal and reforming process of subsequent technique, certain pressure is applied with to battery core, because sodium piece is softer, ductility is preferable, and the original width of sodium piece is equal with pole piece, leading to part sodium is more than first starting sheet width, and this battery core is easy to appear sodium dendrite during following cycle and pierces through diaphragm.Or local micro-short circuit is caused, cycle performance is caused centainly to damage.Therefore, in the preferred technical solution of the application, the technical solution of a≤98%b is selected, can avoid the generation of problem above；
And sodium deficiency is obviously mended in the pole piece border district in sodium-ion battery 5, and the first effect of sodium-ion battery 5 is significantly lower than sodium-ion battery 1, the difference is that sodium piece is different from the width ratio of first starting sheet.Therefore when sodium piece width is less than 80% or more of first starting sheet width, the sodium that may cause border district can not be spread in the short time, and there is pole piece to mend the non-uniform trend of sodium.Therefore, preferred in the application
In technical solution, the technical solution of 80b%≤a is selected, can avoid the generation of problem above；
To sum up, the more preferable 90b%≤a of the application≤98%b range.
(3) compare sodium-ion battery 7~10, when sodium piece is identical with active material, applies certain pressure ratio after being covered with sodium piece and do not apply pressure (sodium-ion battery 8) to the first effect of pole piece with certain improvement effect.This is because increasing pressure can be improved the contact of sodium piece with initial diaphragm, accelerate absorption of the active material to sodium.The pole piece of sodium-ion battery 9 is observed, although its head effect improves when pressure reaches 1.5Mpa, there is a phenomenon where obvious deformation, the homogeneity declines of pole piece for the partial region of pole piece.Therefore, if pressure, which continues to increase, can have the trend for influencing battery core cycle performance.Therefore the pressure applied should be controlled in 0.01~1.5Mpa；Preferably, pressure is 0.2~1.0Mpa.
(4) compare sodium-ion battery 11~13, find when sodium piece thickness is larger, although first effect increases than first starting sheet, head effect is lower than sodium-ion battery 10.Compare the pole piece under its fully charged state, the pole piece of discovery sodium-ion battery 12,13 still has sodium production in part to stay, illustrates that electrolyte permeability is slower when sodium piece is blocked up, have certain influence to its assimilation effect.Compare other sodium-ion batteries, the thickness of sodium piece should be controlled at 1~500 μm, it is preferred that with a thickness of 10~100 μm.
(4) compare sodium-ion battery 14~16, using cathode richness sodium pole piece, head effect is also obviously improved, and reaches estimated sodium supplementing amount.Illustrate that anode mends sodium and battery core first charge-discharge coulombic efficiency equally can be improved.Compare sodium-ion battery 1, sodium-ion battery 14 is identical as its anode and cathode material, and the coulombic efficiency of sodium-ion battery 14 and the coulombic efficiency of sodium-ion battery 1 are not much different, illustrate to have no significant difference using the effect for mending sodium or anode benefit sodium in cathode, it can achieve and mend sodium effect, the pole piece of the sodium-ion battery 14 under fully charged state is dismantled, cathode anode surface is precipitated without obvious sodium, and interface homogeneity is good.Illustrate that mending sodium by the way of rich sodium cathode pole piece equally can achieve effect, and non-evident effect.
(5) compare sodium-ion battery 1 and comparison sodium-ion battery 6~7, it is almost the same to the sodium supplementing amount of same anode, and first effect has no significant difference, illustrate the sodium piece in the present invention mend sodium can with vapor deposition or electrolysis etc. chemical methodes are same controls its sodium supplementing amount.And the time for preparing the rich sodium pole piece of identical sodium supplementing amount is compared, includes covering sodium piece to need 5 minutes or so time with pole piece and the process of cold pressing, and the sodium piece vapour deposition method of same content and galvanoplastic time will more long in the present invention.The technique preparation of rich sodium pole piece provided herein is simple, and while saving time cost, its sodium supplementing amount can be effectively controlled.
(6) compare sodium-ion battery 1 and compare the cycle performance of sodium-ion battery 1, the application is rich
The cycle performance of the battery of sodium pole piece is much higher than comparison sodium-ion battery 1.Illustrate that the application by mending sodium to pole piece, can get through the path of sodium ion in anode material, make 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.
In conclusion the rich sodium pole piece of the sodium-ion battery of the application can effectively improve the coulombic efficiency for the first time and cycle performance of battery core, improve its chemical property.The rich sodium pole piece of the application can realize uniform benefit sodium, and control sodium supplementing amount that can be accurate, easy.The rich sodium pole piece preparation process of the application is simple, and environment is simple, without by pole piece high-temperature operation or contacting other chemicals, avoids the harm that potentiality is brought to pole piece, and low in cost, easy to operate, is conducive to industrialized production.
According to the disclosure and teachings of the above specification, the application those skilled in the art can also make appropriate changes and modifications to the above embodiments.Therefore, the application is not limited to specific embodiment disclosed and described above, should also be as falling into the protection scope of claims hereof to some modifications and changes of the application.In addition, these terms are merely for convenience of description although using some specific terms in this specification, any restrictions are not constituted to the application.
Claims (15)
- A kind of sodium-ion battery pole piece, which is characterized in that the sodium-ion battery pole piece includes sodium piece, collector and the diaphragm being attached on the collector, and the collector and the diaphragm form just starting sheet, and the sodium piece is set on the just starting sheet.
- Sodium-ion battery pole piece according to claim 1, which is characterized in that the sodium piece is incorporated on the just starting sheet through cold pressing.
- Sodium-ion battery pole piece according to claim 1 or 2, which is characterized in that the sodium piece with a thickness of 1 μm~500 μm, preferably 5 μm~100 μm.
- Sodium-ion battery pole piece described in any claim according to claim 1~3, which is characterized in that the width of the sodium piece is a, and the width of the just starting sheet is b, a≤b；Preferably, 80%b≤a≤b；It is furthermore preferred that 80%b≤a≤98%b.
- Sodium-ion battery pole piece described in any claim according to claim 1~4, which is characterized in that the sodium piece is set to the middle part of the initial sodium piece.
- Sodium-ion battery pole piece according to claim 1, which is characterized in that the collector is selected from one of aluminium foil, copper foil, stainless steel foil, porous aluminium foil, porous copper foil, porous stainless steel foil.
- Sodium-ion battery pole piece according to claim 1, which is characterized in that the just starting sheet includes initial anode pole piece and initial cathode sheet.
- Sodium-ion battery pole piece according to claim 7, which is characterized in that the benefit sodium capacity of the amount containing sodium of the sodium piece and the initial anode pole piece is adapted.
- Sodium-ion battery pole piece according to claim 1, which is characterized in that contain anode active material, binder and conductive agent in the diaphragm of 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
- Sodium-ion battery pole piece according to claim 9, 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 mistake Metal oxide and the chemical formula for crossing plating metal sulfide are 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 preparation method of the sodium-ion battery pole piece as described in claim 1~10 any claim, at least includes the following steps:Just starting sheet is prepared, in dry environment, the sodium piece is covered in the membrane surface of the just starting sheet to get the sodium-ion battery pole piece.
- Preparation method according to claim 11, which is characterized in that be cold-pressed after the sodium piece is covered in the just membrane surface of starting sheet.
- Preparation method according to claim 12, which is characterized in that the pressure of the cold pressing is 0.01~1.5Mpa；Preferably, pressure is 0.2~1.0Mpa.
- Preparation method according to claim 11, it is characterized in that, it is described just starting sheet the preparation method comprises the following steps: active material, conductive agent, binder and stirring solvent are uniformly obtained slurry, on a current collector by slurry coating, by drying, just starting sheet is obtained after cold pressing, wherein the slurry coated on a current collector becomes diaphragm after drying cold pressing.
- A kind of sodium-ion battery, including anode pole piece, cathode pole piece, the isolation film and electrolyte being interval between the anode pole piece and the cathode pole piece, it is characterized in that, the anode pole piece and/or cathode pole piece are sodium-ion battery pole piece described in claim 1~10 any claim.
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| PCT/CN2016/090329 WO2018014165A1 (en) | 2016-07-18 | 2016-07-18 | Sodium ion battery electrode sheet, preparation method therefor, and sodium ion battery having electrode sheet |
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| CN110165218A (en) * | 2019-04-04 | 2019-08-23 | 中南大学 | A kind of positive application for mending sodium agent in sodium-ion battery |
| CN113707850A (en) * | 2021-08-30 | 2021-11-26 | 清华大学深圳国际研究生院 | Anode and preparation method thereof, and sodium metal full cell |
| 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 |
| WO2024198297A1 (en) * | 2023-03-29 | 2024-10-03 | 宁德时代新能源科技股份有限公司 | Positive electrode sheet and preparation method therefor, and battery and electric device |
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| CN115036444B (en) * | 2021-03-03 | 2024-06-18 | 厦门稀土材料研究所 | Pre-lithiation and pre-sodiumization composite anode material and preparation method and application thereof |
| CN114709368A (en) * | 2021-06-26 | 2022-07-05 | 宁德时代新能源科技股份有限公司 | Negative pole piece of sodium ion battery, electrochemical device and electronic equipment |
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| CN109565037B (en) | 2022-03-08 |
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