CN109728251A - Positive plate and sodium-ion battery - Google Patents

Positive plate and sodium-ion battery Download PDF

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Publication number
CN109728251A
CN109728251A CN201711036959.0A CN201711036959A CN109728251A CN 109728251 A CN109728251 A CN 109728251A CN 201711036959 A CN201711036959 A CN 201711036959A CN 109728251 A CN109728251 A CN 109728251A
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China
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particle
sodium
positive
ion battery
partial size
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CN201711036959.0A
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苏硕剑
郭永胜
梁成都
王喜庆
王莹
刘倩
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宁德时代新能源科技股份有限公司
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Publication of CN109728251A publication Critical patent/CN109728251A/en

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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

This application provides a kind of positive plate and sodium-ion batteries.The positive plate includes plus plate current-collecting body and positive diaphragm.The anode diaphragm includes positive electrode and is set on the plus plate current-collecting body.The molecular formula of the positive electrode is NaxM[M′(CN)6]y·zH2O, wherein M is transition metal, and M ' is transition metal, 0 < x≤2,0.8≤y < 1,0 < z≤20.The positive electrode includes the first particle and the second particle, and the partial size D50 of first particle is 1 μm~5 μm, and the partial size D50 of second particle is 0.02 μm~0.8 μm.Include prussian blue material in the positive plate of the application, and by the way of large-size particles and small size particle cooperation, cathode film piece compacted density with higher can be made, while making sodium-ion battery that there is preferable high rate performance.

Description

Positive plate and sodium-ion battery

Technical field

This application involves field of batteries more particularly to a kind of positive plates and sodium-ion battery.

Background technique

Since lithium ion battery commercialization, lithium ion battery is with its high-energy density, long circulation life, high safety The advantages such as property have rapidly become the primary selection of the equipment energy-storage travelling wave tube such as computer, electric tool, digital camera.In recent years, with The rapid emergence in electric vehicle market, lithium ion battery have obtained wider application.But with answering extensively for lithium ion battery Be unevenly distributed with, lithium resource, resource relative shortage the problems such as gradually highlight.Currently, possessing the lithium ion battery of high-energy density It is still the first choice in electric vehicle market, but requires relatively low energy storage market and low-speed electronic car market for energy density, The lithium ion battery that price gradually rises will no longer be optimal selection.Therefore in energy storage field and low-speed electronic vehicle field, urgently A kind of novel battery system of low cost need to be developed to replace lithium ion battery.

Compared with lithium, sodium resource distribution is extensive, resourceful, with the advantage in terms of resource and cost, so being with sodium The sodium-ion battery cost that base growth is got up is significantly less than lithium ion battery.Compared with lithium metal, the comparative electrode of metallic sodium The high about 0.3V of potential causes the energy density of sodium-ion battery lower than lithium ion battery, but in extensive energy storage field and low speed Electric automobiles, cycle life and cost are only the factor of overriding concern, rather than energy density, therefore the lower sodium ion of cost Battery is expected to replace lithium ion battery applications in extensive energy storage field and low-speed electronic vehicle field.The radius of lithium ion is about 0.068nm, and the radius of sodium ion about 0.097nm, bigger than lithium ion nearly one third, though it is foreseeable that sodium ion ratio Lithium ion is more difficult to carry out deintercalation in pole piece, therefore the high rate performance of sodium-ion battery will certainly be influenced by very big.In view of This, it is necessory to provide a kind of sodium-ion battery with preferable high rate performance.

Summary of the invention

In view of the problems in the background art, the application is designed to provide a kind of positive plate and sodium-ion battery, The sodium-ion battery has preferable high rate performance.

In order to achieve the above object, in the one side of the application, this application provides a kind of positive plates comprising anode Collector and positive diaphragm.The anode diaphragm includes positive electrode and is set on the plus plate current-collecting body.The anode The molecular formula of material is NaxM[M′(CN)6]y·zH2O, wherein M is transition metal, and M ' is transition metal, 0 < x≤2,0.8≤y < 1,0 < z≤20.The positive electrode includes the first particle and the second particle, and the partial size D50 of first particle is 1 μm~5 μ M, the partial size D50 of second particle are 0.02 μm~0.8 μm.

In the another aspect of the application, this application provides a kind of sodium-ion batteries comprising the application one side is just Pole piece.

Compared with the existing technology, the application has the beneficial effect that

It include prussian blue material Na in the positive plate of the applicationxM[M′(CN)6]y·zH2O, and use big partial size The mode of grain and small size particle cooperation, can make cathode film piece compacted density with higher, while have sodium-ion battery There is preferable high rate performance.

Detailed description of the invention

Fig. 1 is the high rate performance test curve of embodiment 3 and comparative example 6.

Specific embodiment

The following detailed description of the positive plate and sodium-ion battery according to the application.

Illustrate the positive plate according to the application first aspect first.

Positive plate according to the application first aspect includes plus plate current-collecting body and positive diaphragm.The anode diaphragm packet It includes positive electrode and is set on the plus plate current-collecting body.The molecular formula of the positive electrode is NaxM[M′(CN)6]y· zH2O, wherein M is transition metal, and M ' is transition metal, 0 < x≤2,0.8≤y < 1,0 < z≤20.The positive electrode includes the One particle and the second particle, the partial size D50 of first particle are 1 μm~5 μm, and the partial size D50 of second particle is 0.02 μm~0.8 μm.

In the positive plate according to the application first aspect, the positive electrode particle of different-grain diameter is used in mixed way, It is remarkably improved the high rate performance of sodium-ion battery.This is primarily due in positive plate preparation process, if be used only partial size compared with The first big particle, because of NaxM[M′(CN)6]y·zH2The electronic conductivity of O material itself is poor, and the first particle and Often there is biggish gap, the contact defective tightness between particle and particle, the transmission road of ion and electronics between one particle Diameter can also be elongated, and when carrying out charge and discharge under larger current, sodium ion, which has little time to be diffused into material internal, completes charge and discharge Process, electronics has little time to be transmitted to positive electrode surface and has completed charge and discharge process, therefore the high rate performance of sodium-ion battery It is poor.If lesser second particle of partial size is used only, on the one hand, slurry preparation process may have biggish difficulty, reason Often liquid absorption amount is bigger for the second particle for being compared with small particle, needs to be added a large amount of solvent, therefore will cause consolidating for slurry Content is lower or viscosity is too small and can not be coated；On the other hand, it is hardly resulted in using only lesser second particle of partial size The biggish positive diaphragm of compacted density, and the lesser second particle reaction activity of partial size is too high, and excessive pair occurs with electrolyte Reaction, the product of side reaction, which can be covered on positive plate surface, reduces electron conduction and ionic conductivity, also will affect sodium ion The high rate performance of battery.And when biggish first particle of partial size and lesser second particle of partial size are used in combination, partial size compared with The second small particle can fill up make into the gap formed between the first particle and the first particle the particle of positive electrode with Contact between particle becomes more closely, and ion transmission path becomes shorter, electron conduction become more preferably, so as to so that Sodium-ion battery has better high rate performance, while can also be obviously improved the compacted density of positive diaphragm, improves sodium ion electricity The energy density in pond.

In the positive plate according to the application first aspect, it is preferable that the partial size D50 of first particle is 1.5 ~3 μm, the partial size D50 of second particle is 0.1~0.5 μm.

In the positive plate according to the application first aspect, first particle can be second particle form, described Second particle can also be second particle form.

In the positive plate according to the application first aspect, it is preferable that M can be selected from Mn, Fe, Co, Ni, Cu, Zn, V, one of Cr, Ti, Sn, Cd, Pb, Rb.

In the positive plate according to the application first aspect, it is preferable that M ' can be selected from Mn, Fe, Co, Ni, Cu, Zn, V, one of Cr, Ti, Sn, Cd, Pb, Rb.

In the positive plate according to the application first aspect, if the specific surface area of the first particle is excessive, reaction is lived Property increase, with electrolyte occur side reaction probability increase, so that the performance improvement to sodium-ion battery is unfavorable；First particle Specific surface area it is too small, become smaller with the area of electrolyte contacts, Charge-transfer resistance increase, the internal resistance of cell increase, can also make sodium The high rate performance of ion battery declines.Preferably, the specific surface area of first particle is 3m2/ g~15m2/g。

In the positive plate according to the application first aspect, if the specific surface area of the second particle is excessive, reaction is lived Property sharply increase, with electrolyte occur side reaction probability increase, so that the performance improvement to sodium-ion battery is unfavorable；Second The specific surface area of particle is too small, then means that its partial size may be relatively large, be unfavorable for filling up the first particle and the first granulated At gap.The specific surface area of second particle is 10m2/ g~30m2/g。

In the positive plate according to the application first aspect, the main function of the second particle is for filling up first The gap formed between particle and the first particle, usage amount are mainly by the pore size between the first particle and how much to determine It is fixed, therefore usage amount can be selected according to the actual situation.Preferably, the content of second particle is the positive material Expect the 1%~20% of gross mass.It should be pointed out that when the content of the second positive electrode is less than 1%, to sodium-ion battery High rate performance also have improved effect, but effect is than less obvious.

In the positive plate according to the application first aspect, positive electrode is by biggish first particle of partial size and grain The mode that the lesser second particle mixing composition of diameter uses can increase the compacted density of positive diaphragm to a certain extent, thus Promote the energy density of sodium-ion battery.Preferably, the compacted density of the positive diaphragm is 0.5g/cm3~2.0g/cm3, into Preferably, the compacted density of the anode diaphragm is 1.3g/cm to one step3~2.0g/cm3.Here " compacting of positive diaphragm is close Degree " refers to the compacted density of the positive diaphragm on plus plate current-collecting body single side.

In the positive plate according to the application one side, the anode diaphragm may also include binder and conductive agent. The type and content of the binder and conductive agent do not limit specifically, can be selected according to actual needs.Preferably, The binder can be selected from Kynoar, polytetrafluoroethylene (PTFE), polyacrylic acid, polyvinyl alcohol, butadiene-styrene rubber, carboxymethyl cellulose One or more of plain sodium, sodium alginate, polymethylacrylic acid, carboxymethyl chitosan.The content of the binder can be institute State the 1%~10% of positive electrode gross mass.The conductive agent can be selected from acetylene black, conductive black, graphene, carbon filament, stainless One or more of steel fibre, Super-P, carbon nanotube.The content of the conductive agent is the positive electrode gross mass 1%~15%.

In the positive plate according to the application first aspect, the type of the plus plate current-collecting body is not limited specifically System, can be selected according to actual needs.Specifically, the plus plate current-collecting body can be selected from copper foil, aluminium foil, nickel foil, stainless steel One of foil, carbon film, carbon coated aluminum foil.

Secondly explanation sodium-ion battery according to the application second aspect.

Sodium-ion battery according to the application second aspect includes positive plate, negative electrode tab isolation film and electrolyte.Wherein, The positive plate is the positive plate according to the application first aspect.

In the sodium-ion battery according to the application second aspect, the negative electrode tab may include negative current collector with And it is set on negative current collector and the cathode membrane containing negative electrode material.

In the sodium-ion battery according to the application second aspect, the negative electrode tab can also be metallic sodium piece or sodium Alloy sheet.

In the sodium-ion battery according to the application third aspect, the material of the isolation film is unrestricted, can be with It is selected according to actual needs.Specifically, isolation film can be selected from polypropylene screen, polyethylene film, polyethylene/polypropylene/poly- second One or more of the composite membrane of alkene, cellulosic nonwoven fabric film, glass fibre membrane.

Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application and It is not used in limitation scope of the present application.

Embodiment 1

(1) preparation of positive plate

It is Na by molecular formula1.845Mn[Fe(CN)6]0.961·1.988H2O, partial size D50 be 1 μm, specific surface area 12m2/ The first particle and molecular formula of g is Na1.845Mn[Fe(CN)6]0.961·1.988H2O, partial size D50 is 0.3 μm, specific surface area is 20m2The second particle of/g is uniformly mixed, and obtains positive electrode, wherein the content of the second particle is positive electrode gross mass 10%；Then, the positive electrode mixed is mixed for 80:10:10 with solvent with binder, conductive agent according to mass ratio It is even that anode sizing agent is made, wherein binder is Kynoar (PVDF), and conductive agent is conductive carbon black, and solvent is N- methyl pyrrole Pyrrolidone (NMP)；Then, anode sizing agent is coated on the tow sides of plus plate current-collecting body aluminium foil, is then dried, formed just Pole diaphragm；Finally, using positive plate is made after cold pressing, slitting, the corresponding tab of welding, wherein the compacted density of positive diaphragm For 1.8g/cm3。

(2) preparation of negative electrode tab

Negative electrode active material, binder, conductive agent are uniformly mixed system with solvent according to the ratio that weight ratio is 90:5:5 It is standby at negative electrode slurry (wherein negative electrode active material is hard carbon, binder SBR, and conductive agent is conductive carbon black, solvent be go from Sub- water), negative electrode slurry is coated on aluminium foil later, by drying, cold pressing, slitting obtain negative electrode tab.

(3) preparation of electrolyte

Ethylene carbonate (EC), dimethyl carbonate (DMC) are mixed according to volume ratio for 1:1, then will sufficiently be done Dry sodium salt NaClO4It is dissolved in mixed organic solvents, obtains electrolyte, wherein NaClO4Concentration be 1mol/L.

(4) preparation of isolation film

Select routine business polypropylene (PP) film as isolation film.

(5) prepared by sodium-ion battery

It will be fitted into battery packages shell after positive plate, negative electrode tab and isolation film winding, inject electrolyte later, using Sodium-ion battery is made in the techniques such as chemical conversion, standing.

Embodiment 2

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 1.5 μm, specific surface area 11m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.9g/cm3。

Embodiment 3

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.9g/cm3。

Embodiment 4

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 3 μm, specific surface area 8m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.8g/cm3。

Embodiment 5

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 5 μm, specific surface area 5m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.8g/cm3。

Embodiment 6

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 0.02 μm, specific surface area 30m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.8g/cm3。

Embodiment 7

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 0.1 μm, specific surface area 27m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.8g/cm3。

Embodiment 8

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 0.5 μm, specific surface area 18m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.8g/cm3。

Embodiment 9

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 0.8 μm, specific surface area 14m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.7g/cm3。

Embodiment 10

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 20m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 1% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.6g/cm3。

Embodiment 11

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 20m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 20% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.9g/cm3。

Comparative example 1

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 0.5 μm, specific surface area 15m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.2g/cm3。

Comparative example 2

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 8 μm, specific surface area 3m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.3g/cm3。

Comparative example 3

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 1 μm, specific surface area 15m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.3g/cm3。

Comparative example 4

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 30% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.8g/cm3。

Comparative example 5

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 10m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 20m2/g；

The content of second particle is the 0.5% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.1g/cm3。

Comparative example 6

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

It is Na by molecular formula1.845Mn[Fe(CN)6]0.961·1.988H2O, partial size D50 be 2 μm, specific surface area 10m2/ The positive electrode of g is uniformly mixed with solvent for 80:10:10 according to mass ratio with binder, conductive agent and anode sizing agent is made, In, binder is Kynoar (PVDF), and conductive agent is conductive carbon black, and solvent is N-Methyl pyrrolidone (NMP)；Then, Anode sizing agent is coated on the tow sides of plus plate current-collecting body aluminium foil, is then dried, forms positive diaphragm；Finally, using Positive plate is made after cold pressing, slitting, the corresponding tab of welding, wherein the compacted density of positive diaphragm is 1.1g/cm3。

Comparative example 7

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

It is Na by molecular formula1.845Mn[Fe(CN)6]0.961·1.988H2O, partial size D50 is 0.3 μm, specific surface area is 20m2The positive electrode of/g is uniformly mixed with solvent for 80:10:10 according to mass ratio with binder, conductive agent and positive slurry is made Material, wherein binder is Kynoar (PVDF), and conductive agent is conductive carbon black, and solvent is N-Methyl pyrrolidone (NMP)； Then, anode sizing agent is coated on the tow sides of plus plate current-collecting body aluminium foil, is then dried, form positive diaphragm；Finally, Using obtained positive plate after cold pressing, slitting, the corresponding tab of welding, wherein the compacted density of positive diaphragm is 1.6g/cm3。

Comparative example 8

With embodiment 1, difference is the preparation process of sodium-ion battery,

(1) preparation of positive plate

The partial size D50 of first particle is 2 μm, specific surface area 20m2/g；

The partial size D50 of second particle is 0.3 μm, specific surface area 35m2/g；

The content of second particle is the 10% of positive electrode gross mass；

The compacted density of positive diaphragm is 1.9g/cm3。

The parameter of table 1 embodiment 1-11 and comparative example 1-8

Next above-mentioned sodium-ion battery is tested.

(1) the high rate performance test of sodium-ion battery

High rate performance test is carried out to above-mentioned sodium-ion battery.Size of current used be respectively 0.1C, 0.2C, 0.5C, 1C, wherein 1C=170mAh/g, the blanking voltage of charge and discharge are 2.0V~4.0V.Testing procedure is, by sodium-ion battery to set Determining multiplying power constant-current charge to voltage is 4.0V, is later 0.2C with 4.0V constant-voltage charge to electric current, stands 5min later, to set Determining multiplying power constant-current discharge to voltage is 2.0V, then stands 5min, this is a cycle charge discharge electric process, and 5 circulations are calculated The multiplying power discharging capacity ratio of sodium-ion battery after charge and discharge.With the test result of 0.1C for 100%.

The performance test results of table 2 embodiment 1-11 and comparative example 1-8

In comparative example 6, using only the first particle that partial size D50 is 2 μm as positive electrode, the multiplying power of sodium-ion battery Performance is poor, while the compacted density of positive diaphragm is relatively low.In comparative example 7, using only second that partial size D50 is 0.3 μm Grain is used as positive electrode, and the high rate performance of sodium-ion battery is also poor.In embodiment 1-11, biggish first using partial size As positive electrode, the high rate performance of sodium-ion battery is significantly improved the mixture of grain and lesser second particle of partial size, The compacted density of positive diaphragm also has biggish promotion simultaneously.The reason is that, if be used only the first particle, due to its partial size compared with Greatly, often there is biggish gap between particle and particle, the contact between particle and particle is not close, therefore positive diaphragm Compacted density is very low, and when such positive plate carries out charge and discharge under larger current, electron-transport is excessively slow, and electronics has little time to pass Transporting to positive electrode surface would have been completed charge and discharge process, therefore the high rate performance of sodium-ion battery is poor；If being used only the Two particles, then its reactivity is too high, excessive side reaction occurs with electrolyte, the product of side reaction can be covered on positive plate Surface reduces electron conduction and ionic conductivity, equally also will affect the performance of sodium-ion battery high rate performance；When second When grain is used in combination with the first particle, lesser second particle of partial size can be filled into shape between the first particle and the first particle At gap in, become more closely the contact between particle and particle, ion transmission path becomes shorter, electron conduction Become more preferable, so sodium-ion battery has better high rate performance, while positive diaphragm also has bigger compacted density. In conjunction with Fig. 1, compared with comparative example 6, the sodium-ion battery of embodiment 3 shows better high rate performance.

In comparative example 1, the partial size D50 of the first particle is smaller, is not much different with the partial size D50 of the second particle, sodium ion electricity The high rate performance in pond is poor, and the compacted density of positive diaphragm is not also obviously improved, the reason is that, the first particle and second The partial size D50 of particle is not much different, and the second particle is difficult to fill up into the gap between the first particle and the first particle, institute There is no biggish promotion with compacted density, and will lead to reactivity increase since the partial size D50 of the first particle is too small, thus Increase the probability that side reaction in charge and discharge process occurs, the product of side reaction, which is covered on positive plate surface and reduces electronics, leads Electrical property and ionic conductivity, so the high rate performance of sodium-ion battery is bad.In comparative example 2, the partial size D50 mistake of the first particle Greatly, the high rate performance of sodium-ion battery can also be deteriorated, the reason is that, if the partial size D50 of the first particle is excessive, electron conduction It can be deteriorated, sodium ion transmission path is elongated, and sodium ion, which has little time to be diffused into material internal, under larger current completes charge and discharge Electric process, therefore the high rate performance of sodium-ion battery is poor.

In principle, as long as the partial size D50 of the second particle is smaller than the gap that the first particle and the first particle are formed, but The second particle that unlimited small particle can not be obtained when actually synthesizing, when the partial size D50 of the second particle is too small, uniformly Be dispersed in water, it is difficult to separate.

In comparative example 3, if the partial size D50 of the second particle is excessive, size may be more than inside positive plate by first Particle shape at gap size, so that the effect in gap that filling is formed by the first particle be not achieved, can not play raising sodium from The purpose of sub- battery high rate performance can not also play the purpose for improving positive diaphragm compacted density.

In comparative example 5, the content of the second particle is less, and the high rate performance of sodium-ion battery is poor, the compacting of positive diaphragm Density does not also significantly improve, the reason is that, when the second particle is less, there is no and plays inside filling positive plate by the The effect in the gap that one particle is formed, thus the compacted density of improvement and positive diaphragm to the high rate performance of sodium-ion battery Promotion it is very little.In comparative example 4, if the content of the second particle is excessive, it can also deteriorate the forthright again of sodium-ion battery Can, the reason is that, on the one hand, the particle and particle of positive electrode in the positive diaphragm that the second excessive particle will lead to Between contact too closely, electrolyte is difficult to sufficiently infiltrate it, and the transmission of sodium ion is obstructed, therefore sodium-ion battery High rate performance it is poor；On the other hand, the second extra particle (fails to fill the part in the gap formed by the first particle Two particles) it exposes in the electrolytic solution, cause more side reaction, side reaction product, which is covered on positive plate surface, reduces electronics Electric conductivity and ionic conductivity, so the high rate performance of sodium-ion battery is poor.

It analyzes and also knows in embodiment 1-11 and comparative example 8, select moderate the first particle of specific surface area and second Grain, while by size particles hybrid optimization, the high rate performance of sodium-ion battery can be advanced optimized.If first selected The specific surface area of grain and the second particle is excessive, is also more difficult to get even by size particles mixing with preferable high rate performance Sodium-ion battery.This is primarily due to easily cause more side reaction after specific surface area is too big, to can deteriorate sodium ion The high rate performance of battery.And specific surface area is too small, then it should be evident that it be easy to cause contact of the positive electrode with electrolyte Area is too small, so that the high rate performance of sodium-ion battery can also declined.

Claims (10)

1. a kind of positive plate, comprising:
Plus plate current-collecting body；And
Positive diaphragm, including positive electrode and be set on the plus plate current-collecting body；
It is characterized in that,
The molecular formula of the positive electrode is NaxM[M′(CN)6]y·zH2O, wherein M is transition metal, and M ' is transition metal, 0 < x ≤ 2,0.8≤y < 1,0 < z≤20；
The positive electrode includes the first particle and the second particle, and the partial size D50 of first particle is 1 μm~5 μm, and described the The partial size D50 of two particles is 0.02 μm~0.8 μm.
2. positive plate according to claim 1, which is characterized in that the partial size D50 of first particle is 1.5 μm~3 μm； The partial size D50 of second particle is 0.1 μm~0.5 μm.
3. positive plate according to claim 1, which is characterized in that the second particle is filled up into the first particle and the first particle Between gap in.
4. positive plate according to claim 1, which is characterized in that first particle is second particle form, described the Two particles are second particle form.
5. positive plate according to claim 1, which is characterized in that the specific surface area of first particle is 3m2/ g~ 15m2/ g, the specific surface area of second particle are 10m2/ g~30m2/g。
6. positive plate according to claim 1, which is characterized in that the content of second particle is that the positive electrode is total The 1%~20% of quality.
7. positive plate according to claim 1, which is characterized in that the compacted density of the anode diaphragm is 0.5g/cm3~ 2.0g/cm3, it is preferable that the compacted density of the anode diaphragm is 1.3g/cm3~2.0g/cm3。
8. positive plate according to claim 1, which is characterized in that
M is selected from one of Mn, Fe, Co, Ni, Cu, Zn, V, Cr, Ti, Sn, Cd, Pb, Rb；
M ' is selected from one of Mn, Fe, Co, Ni, Cu, Zn, V, Cr, Ti, Sn, Cd, Pb, Rb.
9. positive plate according to claim 1, which is characterized in that the anode diaphragm further includes binder and conductive agent.
10. a kind of sodium-ion battery, which is characterized in that including positive plate of any of claims 1-9.
CN201711036959.0A 2017-10-30 2017-10-30 Positive plate and sodium-ion battery CN109728251A (en)

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