CN108899499A - Based on phosphatic negative electrode material of Sb/Sn and preparation method thereof and the application in sodium-ion battery - Google Patents
Based on phosphatic negative electrode material of Sb/Sn and preparation method thereof and the application in sodium-ion battery Download PDFInfo
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Abstract
The present invention relates to based on phosphatic negative electrode material of Sb/Sn and preparation method thereof and the application in sodium-ion battery, wherein the phosphate negative electrode material based on Sb is SbPO4/ rGO material, the SbPO4/ rGO material is to have SbPO in graphene nano on piece homoepitaxial4Nanometer rods；It is SnP based on the phosphatic negative electrode material of Sn2O7/ rGO material, the SnP2O7/ rGO material is to have SnP in graphene nano on piece homoepitaxial2O7Nano particle；Negative electrode material of the invention increases electric conductivity using graphene as base material, is conducive to the transmission of charge, to be conducive to electrochemical properties.With good cycle performance and high rate performance.It is assembled into after full battery, SbPO4Even if/rGO material is in 1.2kW Kg‑1Power density under, also have up to 99.8Wh Kg‑1Energy density.SnP2O7/ rGO material is in 0.049kW Kg‑1Power density under, energy density is up to 120.8Wh kg‑1。
Description
Technical field：
The present invention provide it is a kind of based on phosphatic negative electrode material of Sb/Sn and preparation method thereof in sodium-ion battery
Using belonging to sodium-ion battery technical field.
Background technique：
Lithium ion battery has been received significant attention as a kind of novel energy-storing equipment.The lithium ion battery of business is negative at present
Pole material is graphite, and theoretical specific capacity is lower, and energy density is unable to satisfy high-power electric appliance as the requirement of electric car etc..With this
Meanwhile content of the lithium resource in the earth is deficient and is unevenly distributed, and limits lithium ion battery in large-scale energy storage device
Development.In contrast, although sodium-ion battery energy density is lower, rich content in nature, chemically with lithium
Can it is similar, sodium-ion battery is similar to the composition of lithium ion battery, principle, and has many advantages, such as to be easily purified, increasingly by
The favor of researcher.But due to sodium ion radiusThan lithium ion radiusGreatly, so that sodium ion exists
Deintercalation and transmission relative difficulty in lattice, therefore find the sodium ion cathode material of high capacity, long circulation life, excellent high rate performance
Material is still the challenge faced at present.
Relative to the negative electrode material (ACS Nano2018,12,1887) of deintercalation mechanism, the negative electrode material of alloy mechanism possesses
Higher theoretical specific capacity and security performance；Relative to the negative electrode material (Nano Energy 2016,19,279) shifted to new management mechanisms,
The negative electrode material of alloy mechanism has lower electrochemical potentials (Nanolett.2012,12,3783), thus in the full electricity of assembling
There is higher energy density and power density when pond.It is a kind of sodium cell negative pole material of great application potential.But it
Also have itself defect, for example during deintercalation sodium, Volumetric expansion is larger, and structure is caused to be easier to collapse, thus
So that cyclical stability is deteriorated.Modification for the negative electrode material of alloy mechanism is the key points and difficulties studied at present
(Sci.Rep.2015,5,8418)。
Relative to the P of alloy mechanism, the negative electrode materials such as Si (Adv.Energy Mater.2017,8,1701827) are based on
The negative electrode material of Sb and Sn has higher electric conductivity and small polarizing voltage, thus the high rate performance that can have been shown.But
The oxide and sulfide of Sb and Sn, the product Na in its charge and discharge process2O and Na2The conduction of S is poor, while among these
Product can be dissolved in electrolyte, cause its cycle performance and high rate performance poor (Adv.Funct.Mater.2015,25,214).Thus
The phosphate compounds of Sb and Sn causes our concern, and main advantage has the following：First, the electricity that they have had
Chemical activity and be safe and non-toxic green material (Chem.Mater.2015,27,6668).Second, in charge and discharge process
In intermediate product Na3PO4The Volumetric expansion in cyclic process can be alleviated as a kind of ion conductor and slow down Na+'s
Diffusional resistance is conducive to the performance (Phys.Rev.B 2004,70,064302) of its chemical property.Third, phosphate is anti-
Three-dimensional electron channel can be formed during answering, substantially increase reaction efficiency (J.Power Sources 2016,331,
16).In conclusion research phosphatic to Sb and Sn is very significant.
Summary of the invention：
In view of the deficiencies of the prior art, the present invention provides a kind of based on the phosphatic negative electrode material of Sb/Sn and its preparation side
Method and the application in sodium-ion battery.
SbPO4It is a kind of material of layer structure, big interlamellar spacingBe conducive to Na+Diffusion to being promoted
The dynamics of reaction.SnP2O7It is a kind of cubic structure, SbPO4Or SnP2O7With graphene it is compound after show excellent electricity
Chemical property, either after the circle of circulation 1000, or the charge and discharge under high current density, there is very high capacity to keep
Rate.It is applied in sodium-ion battery, there is stable cycle performance and high energy and power density.
Technical scheme is as follows：
One kind being based on the phosphatic negative electrode material of Sb/Sn, wherein the phosphate negative electrode material based on Sb is SbPO4/rGO
Material, the SbPO4/ rGO material is to have SbPO in graphene nano on piece homoepitaxial4Nanometer rods；It is phosphatic based on Sn
Negative electrode material is SnP2O7/ rGO material, the SnP2O7/ rGO material is to have SnP in graphene nano on piece homoepitaxial2O7
Nano particle；Content based on graphene in the phosphatic negative electrode material of Sb/Sn is 12-18%.
It is preferred according to the present invention, SbPO4The length of nanometer rods is 90-120nm, SnP2O7Nano particle diameter is 40-
60nm。
According to the present invention, a kind of preparation method based on the phosphatic negative electrode material of Sb/Sn, including steps are as follows：
(1) it disperses graphene in solvent, addition antimony source or tin source, phosphorus source, after heating for dissolving, at 100-120 DEG C
Hydro-thermal reaction 4-6 hours,
(2) ethyl alcohol is successively carried out after the reaction product centrifugation of step (1) to wash, wash, be then dried in vacuo, finally in inertia
Under gas shield, in 400 DEG C of -550 DEG C of high temperature sintering 4-6h, obtain based on the phosphatic negative electrode material of Sb/Sn.
Preferred according to the present invention, in step (1), the antimony source is SbCl3, the tin source is SnCl4·5H2O。
Preferred according to the present invention, in step (1), the phosphorus source is NH4H2PO4。
Preferred according to the present invention, in step (1), the ratio of the additional amount and phosphorus source mole of antimony source or tin source is 1:(1-
3)。
Preferred according to the present invention, in step (1), the solvent is ethylene glycol.
Preferred according to the present invention, in step (1), the additional amount of graphene and the mass volume ratio of solvent are：(4-7)：
(3-5), unit, mg/mL, graphene and the mass ratio in antimony source or tin source are：40-70mg：0.5-2mmol.
Preferred according to the present invention, in step (1), the temperature of hydro-thermal reaction is 110-130 DEG C, reaction time 3-6h.
Preferred according to the present invention, in step (2), vacuum drying temperature is 50-70 DEG C, drying time 10-14h, institute
The inert gas stated is the mixed gas of hydrogen and argon gas, and the volume ratio of hydrogen and argon gas is 95:5
Preferred according to the present invention, in step (2), when antimony source, calcination temperature is 400 DEG C, calcination time 2h；Tin source
When, calcination temperature is 550 DEG C, calcination time 6h.
The above-mentioned application based on the phosphatic negative electrode material of Sb/Sn is applied to sodium-ion battery, negative as sodium-ion battery
Pole materials'use.
It is preferred according to the present invention, it is the sodium-ion battery of negative electrode material based on the phosphatic negative electrode material of Sb/Sn, including
Positive plate, negative electrode tab, diaphragm, electrolyte and shell, the negative electrode tab and positive plate are respectively by active material, conductive agent, viscous
Solvent is added after knot agent mixing, is obtained after wearing into slurry coated on collector；Active material is in sodium-ion battery negative electrode tab
Sb/Sn phosphate, active material is Na in positive plate3V2(PO4)3/C。
It is preferred according to the present invention, what negative electrode tab was prepared as follows：By Sb/Sn phosphate, conductive agent, glue
Tie agent in mass ratio 7:2:N-methyl pyrrolidones is added after 1 ratio mixing, is coated on copper foil after wearing into slurry, coating
It is dried in vacuo at 60 DEG C afterwards, is rolled after dry, be cut into pole piece, the quality of active material is 1.0~1.5mg on unit area
cm-2。
Preferred according to the present invention, positive plate is prepared as follows to obtain：By Na3V2(PO4)3/ C, it conductive agent, glues
Tie agent in mass ratio 8:1:N-methyl pyrrolidones is added after 1 ratio mixing, is coated on aluminium foil after wearing into slurry, coating
It is dried in vacuo at 60 DEG C afterwards, is rolled after dry, be cut into positive plate.
Preferred according to the present invention, the mass ratio of active material and active material in negative electrode tab is controlled 1 in positive plate:
1.2。
Preferred according to the present invention, the electrolyte is NaClO4It is dissolved in propene carbonate, NaClO4Concentration be
1mol/L；Diaphragm material is Whatman GF/F glass microfiber.
The principle of the present invention：
The present invention is by the way that using antimony source or tin source, phosphorus source and GO as raw material, ethylene glycol is solvent, passes through solvent thermal reaction and height
Temperature sintering, respectively obtains SbPO4/ rGO material, SnP2O7/ rGO material considerably increases leading for material using graphene as substrate
Electrically, be conducive to the transmission of electronics, at the same time the functional group on graphene and SbPO4Or SnP2O7Between interaction, can
To prevent the dusting of the particle in cyclic process, to improve chemical property.
Electron ion cell negative electrode material of the invention has following outstanding feature：
(1) sodium ion negative electrode material SbPO of the invention4/ rGO material, SnP2O7/ rGO material, uses graphene for substrate
Material improves the electric conductivity of material, is conducive to the transmission of charge, functional group and SbPO on graphene4Or SnP2O7Between
Interaction can prevent the dusting of electrode material granules, to promote chemical property.
(2) negative electrode material SbPO of the invention4/ rGO material or SnP2O7SbPO on/rGO material4Or SnP2O7It is to receive
Rice grain can reduce the diffusion path of sodium ion, promote kinetics, thus all become the cycle performance dedicated to and multiplying power
Performance.For SbPO4/ rGO material, in 1Ag-1Current density under, circulation 1000 circle also have 100mAh g-1The capacity of left and right.
For SnP2O7/ rGO material, in 1Ag-1Current density under, circulation 1000 circle also have 150mAh g-1The capacity of left and right.
(3) SbPO of the invention4/ rGO material or SnP2O7It is right respectively with original position and means of offing normal on/rGO material
SbPO4Mechanism of intumescence and SbPO of the nanometer rods during embedding sodium4/ rGO or SnP2O7The electrochemical reaction mechanism of/rGO carries out
Deep probes into.SbPO4It is layer structure, interlayer direction is exactly the radial direction of nanometer rods, so when sodium ion insertion
It waits, sodium ion is inserted between layers, and leading to the expansion of nanometer rods is also along radially carrying out.SbPO4The reaction machine of/rGO
Managing in voltage range is 0.01-1.5V test, discharge process SbPO before this4Reduction reaction, the alloying followed by Sb is anti-
It answers, charging process is the removal alloying process of Sb.SnP2O7The reaction mechanism of/rGO is 0.01-2.5V test in voltage range,
Discharge process SnP before this2O7Reduction reaction, followed by the alloying reaction of Sn, charging process is the removal alloying of Sn, then
It is the oxidation process of Sn.But whole process is that part is reversible, is also matched with subsequent electrochemistry circulation.
(4) SbPO of the invention4/ rGO or SnP2O7Half electrical property that/rGO material has had has carried out full battery to it
After assembling, SbPO4Even if/rGO material is in 1.2kW Kg-1Power density under, also have up to 99.8Wh Kg-1Energy density.
SnP2O7/ rGO material is in 0.049kW Kg-1Power density under, energy density is up to 120.8Wh kg-1。
Detailed description of the invention：
Fig. 1 is SbPO made from the embodiment of the present invention 14/ rGO (a) and SnP2O7The XRD diffraction pattern of/rGO (b) material.
Fig. 2 is SbPO made from the embodiment of the present invention 14/ rGO (a) and SnP2O7The stereoscan photograph of/rGO (b) material.
Fig. 3 is SbPO made from the embodiment of the present invention 14/ rGO (a) and SnP2O7The Elemental redistribution photo of/rGO (b) material.
Fig. 4 is SbPO4/rGO (a) made from the embodiment of the present invention 1 and SnP2O7/ rGO (b) material is in sodium ion half-cell
Cycle performance comparison diagram.
Fig. 5 is SbPO made from the embodiment of the present invention 14/ rGO (a) and SnP2O7/ rGO (c) material is in sodium ion full battery
Cycle performance comparison diagram.SbPO4/ rGO (b) and SnP2O7/ rGO (d) is power energy density curve graph.
Specific embodiment：
Below in conjunction with drawings and examples, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Raw material in embodiment is commercial products.
Embodiment 1
SbPO4The preparation of/rGO material, steps are as follows：
(1) 50mgGO is dispersed in the ethylene glycol of 40ml, 1mmol SbCl is added3, 2mmol ammonium dihydrogen phosphate, at 70 DEG C
Dissolution.
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, in 120 DEG C of reaction 4h；
(3) product is centrifuged, and is cleaned for several times with ethyl alcohol, water, 60 DEG C of vacuum oven dry 12h is placed in, by product in argon hydrogen
The lower 400 DEG C of reactions 2h of atmosphere.Obtain SbPO4/rGO。
SnP2O7The preparation of/rGO, steps are as follows：
(1) 50mgGO is dispersed in the ethylene glycol of 40ml, 1mmol SnCl is added4·5H2O, 2mmol ammonium dihydrogen phosphate, 70
It is dissolved at DEG C.
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, in 120 DEG C of reaction 4h；
(3) product is centrifuged, and is cleaned for several times with ethyl alcohol, water, 60 DEG C of vacuum oven dry 12h is placed in, by product in argon hydrogen
The lower 550 DEG C of reactions 6h of atmosphere.Obtain SnP2O7/rGO。
Performance test
To SbPO4/ rGO and SnP2O7/ rGO does XRD test, and diffraction pattern in Fig. 1 (a) as shown in Figure 1, by that can see
Out, all diffraction maximums may both correspond to XRD standard card JCPDS No.29-1352, in Fig. 1 (b) it can be seen from all spread out
Penetrating peak may both correspond to XRD standard card JCPDS No.35-0829.But since the crystallinity of rGO is bad, SbPO4With
SnP2O7Peak mask the diffraction maximum of rGO.To SbPO obtained4/ rGO and SnP2O7/ rGO specimen material does scanning electron microscope point
Analysis, stereoscan photograph as shown in Fig. 2, it can be seen from Fig. 2 (a) SbPO4/ rGO sample is that homoepitaxial is received in graphene
The SbPO of rice on piece4Nanometer rods.Fig. 2 (b) is as can be seen that SnP2O7/ rGO sample is homoepitaxial in graphene nano on piece
SnP2O7Nano particle.To SbPO obtained4/ rGO and SnP2O7/ rGO specimen material is high-resolution-ration transmission electric-lens photo, Fig. 3 (a)
Clearly find out that Elemental redistribution is highly uniform with Fig. 3 (b).
Electrochemical property test
Sodium ion half-cell performance test：
In order to verify SbPO4/ rGO and SnP2O7The electric property of/rGO material, with SbPO4/ rGO or SnP2O7/ rGO material
For negative electrode material, sodium piece assembles sodium ion half-cell for reference electrode and to electrode, characterizes chemical property, cathode preparation：
SbPO4/ rGO and SnP2O7/ rGO material, acetylene black, sodium alginate are dispersed in suitable quantity of water, and hand grinds 30min, and paste is made
Then slurry is coated uniformly on slurry on copper foil, be then dried in vacuo at 60 DEG C；After dried copper foil is rolled, system
At cathode, for sodium piece for reference electrode and to electrode, Whatman GF/F glass microfiber is diaphragm, 1.0M NaClO4It is dissolved in carbon
Acid propylene ester (PC) is electrolyte, is carried out the glove box (Mikrouna, Super 1220/750/900) full of argon gas is inner.
The charge-discharge test of battery is carried out in blue electric (Land CT-2001A) test macro, battery operation interval is 0.01~
1.5V and 0.01~2.5V.Fig. 4 (a) is SbPO made from embodiment 14/ rGO sample and contrast material SbPO4 are for 1Ag-1's
Cyclic curve under high current density, Fig. 4 (b) are SnP made from embodiment 12O7/ rGO sample is for 1Ag-1And 2Ag-1It is big
Cyclic curve under current density.SbPO it can be seen from Fig. 44/ rGO and SnP2O7/ rGO sample is all shown well
Cycle performance.
Sodium ion full battery performance test：
Fig. 5 is full electrical property curve, SbPO4/ rGO (a) and SnP2O7/ rGO (c) assembles the cyclic curve after full battery.From
It can be seen that SbPO in figure4/ rGO and SnP2O7/ rGO has stable cycle performance after assembling full battery.SbPO4/rGO
(b) and SnP2O7/ rGO (d) is power density and energy density profile figure.SbPO4Even if/rGO material is in 1.2kW Kg-1Function
Under rate density, also there is up to 99.8Wh Kg-1Energy density.SnP2O7/ rGO material is in 0.049kW Kg-1Power density
Under, energy density is up to 120.8Wh kg-1。
Comparative example 1
SbPO4The preparation method of material, including steps are as follows：
(1) it by 1mmol potassium antimony tartrate, 2mmol ammonium dihydrogen phosphate, is dissolved at 70 DEG C；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, in 120 DEG C of reaction 4h；
(3) product is centrifuged, and is cleaned for several times with ethyl alcohol, water, 60 DEG C of vacuum oven dry 12h is placed in, by product in argon hydrogen
The lower 400 DEG C of reactions 2h of atmosphere, obtains SbPO4Micron ball, micron ball vary, and dispersion is uneven and has slight reunion existing
As.It is unfavorable for its electrochemical properties.
Comparative example 2
SbPO4The preparation method of/rGO, specific step is as follows：
(1) it disperses 50mgGO in the ethylene glycol of 40ml, is added 1mmol potassium antimony tartrate, 2mmol ammonium dihydrogen phosphate, 70
It is dissolved at DEG C；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, in 120 DEG C of reaction 4h；
(3) product is centrifuged, and is cleaned for several times with ethyl alcohol, water, 60 DEG C of vacuum oven dry 12h is placed in, by product in argon hydrogen
The lower 400 DEG C of reactions 2h of atmosphere, obtains SbPO4/rGO；The comparative example is original with ammonium dihydrogen phosphate using potassium antimony tartrate as antimony source
Material, ethylene glycol is solvent, is obtained by solvent thermal reaction and high temperature sintering, and obtained material pattern is irregular micron compound,
Phosphoric acid antimony and graphene are not combined with each other well, and electric conductivity is deteriorated, and are unfavorable for the transmission of electronics, thus what performance was gone on business
Cycle performance.
Comparative example 3
SbPO4The preparation method of/rGO, specific step is as follows：
(1) 50mgGO is dispersed in the ethylene glycol of 40ml, 1mmol SbCl is added3, 2mmol ammonium dihydrogen phosphate, at 70 DEG C
Dissolution；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, in 120 DEG C of reaction 4h；
(3) product is centrifuged, and is cleaned for several times with ethyl alcohol, water, 60 DEG C of vacuum oven dry 12h is placed in, by product in argon gas
The lower 400 DEG C of reactions 2h of atmosphere, obtains SbPO4/rGO。
The comparative example is calcination under an argon atmosphere, and calcination atmosphere directly affects the reducing degree of graphene, thus directly
Influence electrochemical properties.
Comparative example 4
SnP2O7The preparation method of/rGO, specific step is as follows：
(1) 50mgGO is dispersed in the ethylene glycol of 40ml, 1mmol SnCl is added4·5H2O, 2mmol ammonium dihydrogen phosphate, 70
It is dissolved at DEG C；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, in 120 DEG C of reaction 4h；
(3) product is centrifuged, and is cleaned for several times with ethyl alcohol, water, 60 DEG C of vacuum oven dry 12h is placed in, by product in argon hydrogen
The lower 400 DEG C of reactions 2h of atmosphere.
The comparative example is to obtain SnP in 400 DEG C of calcinations2O7/ rGO, SnP2O7/ rGO crystallinity is very bad, thus electrification
Show the cyclicity gone on business and high rate performance in nature.
Claims (10)
1. one kind is based on the phosphatic negative electrode material of Sb/Sn, wherein the phosphate negative electrode material based on Sb is SbPO4/ rGO material
Material, the SbPO4/ rGO material is to have SbPO in graphene nano on piece homoepitaxial4Nanometer rods；It is phosphatic negative based on Sn
Pole material is SnP2O7/ rGO material, the SnP2O7/ rGO material is to have SnP in graphene nano on piece homoepitaxial2O7It receives
Rice grain；Content based on graphene in the phosphatic negative electrode material of Sb/Sn is 12-18%；SbPO4The length of nanometer rods is
90-120nm, SnP2O7Nano particle diameter is 40-60nm.
2. a kind of preparation method based on the phosphatic negative electrode material of Sb/Sn, including steps are as follows：
(1) it disperses graphene in solvent, addition antimony source or tin source, phosphorus source, after heating for dissolving, the hydro-thermal at 100-120 DEG C
Reaction 4-6 hours,
(2) ethyl alcohol is successively carried out after the reaction product centrifugation of step (1) to wash, wash, be then dried in vacuo, finally in inert gas
Under protection, in 400 DEG C of -550 DEG C of high temperature sintering 4-6h, obtain based on the phosphatic negative electrode material of Sb/Sn.
3. the preparation method according to claim 1 based on the phosphatic negative electrode material of Sb/Sn, which is characterized in that step
(1) in, the antimony source is SbCl3, the tin source is SnCl4·5H2O；The phosphorus source is NH4H2PO4。
4. the preparation method according to claim 1 based on the phosphatic negative electrode material of Sb/Sn, which is characterized in that step
(1) in, the ratio of the additional amount and phosphorus source mole of antimony source or tin source is 1:(1-3), the solvent are ethylene glycol；Graphene
The mass volume ratio of additional amount and solvent is：(4-7)：The mass ratio of (3-5), unit, mg/mL, graphene and antimony source or tin source
For：40-70mg：0.5-2mmol.
5. the preparation method according to claim 1 based on the phosphatic negative electrode material of Sb/Sn, which is characterized in that step
(1) in, the temperature of hydro-thermal reaction is 110-130 DEG C, reaction time 3-6h.
6. the preparation method according to claim 1 based on the phosphatic negative electrode material of Sb/Sn, which is characterized in that step
(2) in, vacuum drying temperature is 50-70 DEG C, drying time 10-14h, and the inert gas is the mixing of hydrogen and argon gas
The volume ratio of gas, hydrogen and argon gas is 95:5.
7. the preparation method according to claim 1 based on the phosphatic negative electrode material of Sb/Sn, which is characterized in that step
(2) in, when antimony source, calcination temperature is 400 DEG C, calcination time 2h；When tin source, calcination temperature is 550 DEG C, and calcination time is
6h。
8. the application described in claim 1 based on the phosphatic negative electrode material of Sb/Sn is applied to sodium-ion battery, as sodium
Ion battery cathode material uses.
9. described in claim 1 is the sodium-ion battery of negative electrode material, including anode based on the phosphatic negative electrode material of Sb/Sn
Piece, negative electrode tab, diaphragm, electrolyte and shell, the negative electrode tab and positive plate are respectively by active material, conductive agent, binder
Solvent is added after mixing, is obtained after wearing into slurry coated on collector；Active material is Sb/Sn in sodium-ion battery negative electrode tab
Phosphate, active material is Na in positive plate3V2(PO4)3/C。
10. it is according to claim 9 based on the phosphatic negative electrode material of Sb/Sn be negative electrode material sodium-ion battery,
It is characterized in that, the mass ratio of active material and active material in negative electrode tab is controlled 1 in positive plate:1.2.
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