CN110096774A - Mechanics impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect - Google Patents
Mechanics impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect Download PDFInfo
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Abstract
The invention discloses the emulation modes that a kind of mechanics impacts lower electrolytic solution for super capacitor ion redistribution effect, method includes the following steps: establishing the stored energy power model of supercapacitor；In stored energy power model, insertion mechanics impacts the migration redistribution model of lower electrolyte ion, to constitute the energy storage based on supercapacitor-shock-sensitive coupling model system；Simulation calculation is carried out to energy storage-shock-sensitive coupling model system using finite element software, to realize that mechanics impacts effective emulation of lower electrolytic solution for super capacitor ion redistribution effect.This method can change the electrolyte ion concentration during impact, the variation of supercapacitor output voltage carries out numerical value calculating, it can be scanned with the important process parameter of capacitor, it is analyzed for the affecting laws of ion redistribution effect conspicuousness, the inhibition or enhancing to supercapacitor mechanics sensitlzing effect can be effectively facilitated, meets it in the application demand of different operating environment.
Description
Technical field
The present invention relates to supercapacitor technologies field, in particular to a kind of mechanics impact lower electrolytic solution for super capacitor from
The emulation mode of sub- redistribution effect.
Background technique
Supercapacitor is a kind of widely used electrochemical energy storing device, it passes through electric double layer effect and faraday's reaction
The advantages such as two kinds of mechanism realize the storage and release of energy, have capacity density big, and high temperature performance is good, has extended cycle life,
It is widely used in the fields such as electric car, industrial detection and wearable electronic device.
Modeling and simulating method plays a significant role the design and exploitation of supercapacitor, can by parameter scanning into
Line number value calculates, and realizes the optimization design to each main design parameters, and part substitutes cumbersome reality needed for traditional design method
Test examination.But supercapacitor modeling and simulating method in the related technology, it is electric under normal temperature and pressure state to only account for it
Chemical characteristic, and the disturbing effect of the environmental factors such as temperature, pressure is had ignored, limit the practical application of this kind of emulation mode.
In fact, in the operating condition can not as supercapacitor is in the gradually application of some field of industry detection
It avoids will receive external mechanics percussion.And supercapacitor internal reservoir has liquid electrolyte, has under percussion
Ion redistribution effect.Therefore, it there is an urgent need for a kind of novel simulated method, realizes and lower supercapacitor electrolysis is impacted to mechanics
Effective emulation of liquid ion redistribution effect.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.
For this purpose, it is an object of the invention to propose that a kind of mechanics impacts lower electrolytic solution for super capacitor ion redistribution effect
Emulation mode, this method implemented by comsol simulation Software Platform, and compatible with matlab emulation platform, is had just
In transplanting, the feasibility expanded.
In order to achieve the above objectives, the invention proposes the emulation mode of electrolytic solution for super capacitor ion redistribution effect,
The following steps are included: establishing the stored energy power model of supercapacitor；In the stored energy power model, insertion mechanics punching
The migration redistribution model of lower electrolyte ion is hit, to constitute the energy storage based on supercapacitor-shock-sensitive coupling model body
System；Simulation calculation is carried out to the energy storage-shock-sensitive coupling model system using finite element software, to realize under mechanics impact
Effective emulation of electrolytic solution for super capacitor ion redistribution effect.
The mechanics of the embodiment of the present invention impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect, description
The generation mechanism and mechanics percussion of supercapacitor electrolyte ion density unevenness weighing apparatus phenomenon in charge and discharge process
The ion concentration redistribution mechanism of generation, and ion concentration redistribution effect is considered to the shadow of supercapacitor electrochemical reaction
Effect is rung, is implemented by COMSOL simulation Software Platform, and compatible with matlab emulation platform, has convenient for transplanting, open up
The feasibility of exhibition；The dynamics to electrolytic solution for super capacitor ion redistribution effect in mechanics impact process may be implemented in turn
Emulation is calculated including the accurate simulation to electrolyte ion concentration, device output voltage；It can work devices such as discharge currents
Parameter is scanned, and analyzes it for the affecting laws of supercapacitor mechanics shock-sensitive characteristic；It can be to the impact moment
Degree of discharge parameter is scanned, and analyzes it for the affecting laws of supercapacitor mechanics shock-sensitive characteristic.
In addition, mechanics according to the above embodiment of the present invention impacts lower electrolytic solution for super capacitor ion redistribution effect
Emulation mode can also have following additional technical characteristic:
Further, in one embodiment of the invention, the stored energy power model includes electric double layer effect model
With faraday's reaction model.
Further, in one embodiment of the invention, the energy storage-shock-sensitive coupling model system includes double electricity
The electrode kinetics model of effect layer, the electrode kinetics model of faraday's reaction, ion diffusion model and power in electrolyte
Learn the electrolyte ion redistribution model under impact.
Further, in one embodiment of the invention, the stored energy power model by electrode active material and
The redox reaction of the high reversible occurred between electrolyte material, so that charge occurs transfer and generates simultaneously storage energy,
In, the faraday's reaction model energy storage is occupied an leading position.
Further, in one embodiment of the invention, by the stored energy power model to electric double layer effect mould
Type carries out faradic currents amendment, so that electric potential field of supercapacitor during charging and discharging, ion concentration field
Variation tendency in the case where two kinds of mechanism of faraday's reaction model and electric double layer effect model drive jointly is determined.
Further, in one embodiment of the invention, moment is impacted in insertion mechanics, electrolyte will be driven by inertia force
Movable property gives birth to directed flow, and the dynamic process of flow field change is described by Navier-Stokes equation:
Wherein, u1, ρ1, μ respectively indicates the flow field velocity of electrolyte flow, density, dynamic viscosity.
Further, in one embodiment of the invention, pass through COMSOL weak form equation and common version partial differential
The complex model construction method of equation, embeds model to lithium ionic cell module and is modified, so that the stored energy power mould
Type meets the energy storage-shock-sensitive coupling model system of building.
Further, in one embodiment of the invention, the common version partial differential equation framework is as follows:
Wherein, u is partial differential equation dependent variable, and t is independent variable, and other parameters are UNIVERSAL COEFFICIENT.
Further, in one embodiment of the invention, special to supercapacitor shock-sensitive using COMSOL software
Property is emulated, and two kinds of shock-sensitive phenomenon occurs under different working modes in the supercapacitor, wherein the first
Situation be when the supercapacitor carry out large current charge when, the rate of kinetic current gain and loss ion be far longer than in solution from
The rate of son diffusion, second situation and the first described situation conversely, because the supercapacitor self discharge effect, from
Sub- concentration distribution has become balanced.
The additional aspect of the present invention and advantage will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect and advantage of the invention will become from the following description of the accompanying drawings of embodiments
Obviously and it is readily appreciated that, in which:
Fig. 1 is the emulation that lower electrolytic solution for super capacitor ion redistribution effect is impacted according to the mechanics of the embodiment of the present invention
Method flow diagram；
Fig. 2 is according to supercapacitor structures schematic diagram in the embodiment of the present invention；
Fig. 3 is according to supercapacitor electric double layer effect principle figure in the embodiment of the present invention；
Fig. 4 is the faraday's reaction schematic diagram according to supercapacitor in the embodiment of the present invention；
Fig. 5 is the ion redistribution schematic diagram according to supercapacitor in the embodiment of the present invention under percussion；
Fig. 6 is the weak form equation entrance schematic diagram according to COMSOL software in the embodiment of the present invention；
Fig. 7 is two kinds of shock-sensitive phenomenon analogous diagrams according to supercapacitor in the embodiment of the present invention, wherein (a) is
The first sensitivity phenomenon: voltage fluctuates downwards, and (b) be second of sensitivity phenomenon: voltage fluctuates upwards；
Fig. 8 is according to the ion distribution analogous diagram in the embodiment of the present invention in supercapacitor impact process, wherein (a)
It (b) is second of sensitivity phenomenon, ts represents the duration of impact in figure for the first sensitivity phenomenon；
Fig. 9 is according to the ultracapacitor voltage peak amplitude under discharge currents different in the embodiment of the present invention and degree of discharge
Analogous diagram；
Figure 10 be according to the ion concentration field analogous diagram of supercapacitor under discharge currents different in the embodiment of the present invention,
In, (a) is discharge current 5mA, (b) is discharge current 20mA；
Figure 11 is the actual measurement shock-sensitive phenomenon variation diagram according to supercapacitor in the embodiment of the present invention, wherein (a) is
The shock-sensitive phenomenon that voltage fluctuates downwards, (b) the shock-sensitive phenomenon fluctuated upwards for voltage.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
The electrolytic solution for super capacitor ion redistribution effect proposed according to embodiments of the present invention is described with reference to the accompanying drawings
Emulation mode and system, the electrolytic solution for super capacitor ion proposed according to embodiments of the present invention is described with reference to the accompanying drawings first
The emulation mode of redistribution effect.
Fig. 1 is the emulation that the mechanics of one embodiment of the invention impacts lower electrolytic solution for super capacitor ion redistribution effect
Method flow diagram.
As shown in Figure 1, the mechanics impact lower electrolytic solution for super capacitor ion redistribution effect emulation mode include with
Lower step:
In step s101, the stored energy power model of supercapacitor is established.
Wherein, stored energy power model includes electric double layer effect model and faraday's reaction model.
Specifically, stored energy power model passes through the high reversible occurred between electrode active material and electrolyte material
Redox reaction so that charge occur transfer generate and storage energy, wherein the energy storage of faraday's reaction model is predominantly
Position.
Further, in one embodiment of the invention, by stored energy power model to electric double layer effect model into
Row faradic currents amendment, so that electric potential field of supercapacitor during charging and discharging, ion concentration field are in faraday
Variation tendency under two kinds of mechanism of reaction model and electric double layer effect model drive jointly is determined.
Specifically, as shown in Fig. 2, the positive and negative anodes of supercapacitor are the porous film material with high-specific surface area,
Centre is separated by diaphragm, and liquid electrolyte is full of in the hole of electrode and diaphragm.The energy storage mechnism of supercapacitor includes double electricity
Two kinds of mechanism of effect layer and Faraday pseudo-capacitance effect, the embodiment of the present invention will carry out respectively modelling by mechanism according to two kinds of mechanism and grind
Study carefully.
As shown in figure 3, porous electrode, which has, forms solid-liquid interface abundant between micropore structure, with electrolyte.
The electric double layer effect energy storage mechanism of supercapacitor is based on negative ions absorption at solid-liquid interface and is formed by electric double layer knot
Structure.
The essence of the charge and discharge process of supercapacitor is the formation and disintegration of microcosmic double electrical layers, and thus generates
Electrode and electrolyte in potential, ion concentration couple variations.Two parts of electrode and diaphragm for supercapacitor, this
Inventive embodiments construct electric field and concentration of electrolyte field model respectively, carry out Dynamic Modeling research.
Firstly, in porous electrode, it can be by electric double layer electric current from the electric current of electrode matrix phase flow direction electrolysis liquid phase
Description,
Wherein, i1Indicate the surface current density of electrolysis liquid phase, iDLIndicate that electric current caused by electric double layer effect is close
Degree.
For electrode matrix phase, the relationship between electric current and potential can be provided by Ohm's law,
Wherein, isFor the surface current density of electrode matrix phase, σs,effThe equivalent conductivity and Ψ of electrode matrix phasesFor electricity
The potential of pole matrix phase.
But for electrolysis liquid phase, need to carry out concentration field amendment to Ohm's law,
Wherein, i1For the surface current density of electrolysis liquid phase, σ1,effFor the equivalent conductivity of electrolysis liquid phase,
Ψ1For the potential of electrolysis liquid phase, t+For the transfer ratio of electrolyte solution, c1For the ion concentration of electrolyte solution, F, R
Faraday constant, universal gas constant and kelvin degree are respectively indicated with T.
In pore media, it is electrolysed the equivalent conductivity σ of liquid phasel,effObey the graceful relationship in Prague namely σ1,eff=σ1
ε1 1.5, wherein σ1For electrolyte ion conductivity, ε1Indicate the porosity of electrode.
The potential equation for being electrolysed liquid phase can be obtained by equation (1) and (3) simultaneous
Due to charge conservation,Always it sets up.By this charge conservation equation and equation (2) simultaneous:
Ion concentration field is influenced by reflection electric current and Ion transfer simultaneously, as shown in equation (6)
Wherein, ε1And D1,effThe porosity of electrode and the ionic diffusion coefficient of electrolyte solution are respectively indicated, when t is indicated
Between.
In membrane portions, since diaphragm matrix is non-conductive, is=0.So availableAnd then it is electrolysed liquid phase
Potential equation can indicate are as follows:
Similar with equation (6), since membrane portions do not have electric double layer reaction, the ion concentration field equation for being electrolysed liquid phase can be with
It is given by,
According to the mechanism of electric double layer effect, electric double layer current density iDLIt can be calculated by following formula[85–87]
Wherein, avIndicate the specific surface area of porous electrode, CdlIndicate capacitance parameter related with electric double layer effect.
In addition, part supercapacitor also carries out the storage and release of energy by faraday's reaction.Faraday is anti-
Should be the high reversible occurred between electrode active material and electrolyte material redox reaction (such as ruthenium-oxide electrode with
Redox reaction between sulfuric acid electrolyte).As shown in figure 4, the receiving and losing electrons effect of redox reaction makes charge
Transfer, to realize the storage of energy.
Faraday's reaction energy storage accounts for the supercapacitor of leading role, and the faradic currents in electrochemical system want long-range
In electric double layer electric current.Therefore, such ultracapacitor energy storage kinetic model need electric double layer energy storage model equation (1)~
(9) a series of amendments are carried out on the basis of.
Firstly, in porous electrode, from the electric current of electrode matrix phase flow direction electrolysis liquid phase by electric double layer electric current and method
Electric current is drawn to collectively form, original equation (1) needs to be added faradic currents item:
Wherein, iFIndicate current density caused by faraday's reaction.
Correspondingly, the electrolysis liquid phase potential equation of equation (4) and the electrode matrix phase potential equation of equation (5) are also required to add
Enter faradic currents correction term:
For ion concentration field described in equation (6), kinetic current item should be total to by electric double layer electric current and faradic currents
Same composition,
And according to electrochemical theory, faradic currents density can be calculated by following formula:
iF=avj1oc (14)
Wherein, j1ocIndicate that faraday's transfer current density, value can be counted by Butler-Volmer equation
It calculates:
Wherein, i0Indicate faraday's exchange current density, αaAnd αcRespectively indicate the transfer ratio of anode and cathode, UocTable
Show the open circuit potential of Faradaic processes.
Electric double layer energy storage model is modified by equation (10)~(15), the embodiment of the present invention has obtained pervasive surpass
The stored energy power model of grade capacitor.By this model, electric potential field of supercapacitor during charging and discharging, from
Change procedure of the sub- concentration field in the case where two kinds of mechanism of faraday's reaction and electric double layer effect drive jointly can be fully defined.
In step s 102, in stored energy power model, insertion mechanics impacts the migration redistribution of lower electrolyte ion
Model, to constitute the energy storage based on supercapacitor-shock-sensitive coupling model system.
Further, in one embodiment of the invention, energy storage-shock-sensitive coupling model system includes electric double layer effect
The electrode kinetics model answered, the electrode kinetics model of faraday's reaction, ion diffusion model and mechanics punching in electrolyte
Electrolyte ion redistribution model under hitting.
It should be noted that stored energy power modeling is the effective ways for studying micro-nano energy device, in supercapacitor
Research field has many applications.The embodiment of the present invention comprehensively considers the storage effect and shock-sensitive effect of supercapacitor,
Carry out integrated Coupling method.
Specifically, carrying out for electrochemical reaction will be constantly in an electricity in the electrochemical system of supercapacitor
Pole generates ion, while in another consumption of electrode ion, total trend be so that the positive and negative electrode of electrolyte intermediate ion it is dense
Degree distribution generation is unbalanced, and constantly accumulates.And on the other hand, ion has diffusion effect in the electrolytic solution, and total trend is
So that the ion concentration in electrolyte equalizes.When the charging and discharging currents of supercapacitor are larger, electrochemical reaction is stronger,
The diffusion effect of electrolyte far will be not enough to ion caused by offsetting reaction process and quickly generate and consume.Therefore, in electrolyte
Ion concentration it is unbalanced will likely be more significant, as shown in Figure 5.
The generation process and its caused shock-sensitive effect of the ion concentration difference in charge and discharge process is specifically described below.
Before charge and discharge start, kinetic current 0, the ion in electrolyte passes through long-term diffusion effect, at equilibrium,
After charge and discharge process starts, the kinetic current symbol of supercapacitor positive and negative electrode is on the contrary, two electrodes obtain respectively
To and lose ion.
For charging process:
For discharge process:
Therefore, after charge or discharge process starts, the ion concentration of positive and negative electrode generates opposite variation, ion concentration
Equilibrium state will be broken, it is poor to generate ion concentration between positive and negative anodes.This ion concentration difference effect is presented as ion
Concentration field has the gradient value of non-zero:
It is impacted moment in acceleration, electrolyte will be generated directed flow, the dynamics of flow field change by inertia power drive
Process can be described by Navier-Stokes equation:
Wherein, u1, ρ1, μ respectively indicates the flow field velocity of electrolyte flow, density, dynamic viscosity.
According to Hydrodynamics Theory it is found that there are ion concentration gradient, electrolyte flow will be in the short time
Inside significantly change ion concentration field distribution, it is therefore desirable to the electrolysis liquid phase ion concentration field kinetic model of equation (13)
Flow field correction term is added,
Similarly, for the ion concentration field equation of membrane portions described in equation (8), it is also desirable to be flowed accordingly
Field amendment,
Equation (20)~(23) constitute electrolytic solution for super capacitor flow field and ion concentration field acceleration shock response mould
Type.It is combined with stored energy power model, supercapacitor is in impact moment by electrolyte ion shock-sensitive effect pair
The complicated coupling change procedure that electrochemical system generates can be by quantitative description.Thus to being that the embodiment of the present invention is subsequent to electrolysis
Liquid bombardment by ions sensitlzing effect carries out simulation study and lays a good foundation.
In step s 103, simulation calculation is carried out to energy storage-shock-sensitive coupling model system using finite element software, with
Realize that mechanics impacts effective emulation of lower electrolytic solution for super capacitor ion redistribution effect.
Wherein, the finite element software that the embodiment of the present invention utilizes is COMSOL software, and COMSOL software is that a function is strong
Big multiple physical field simulation software, what the agent model equation and the embodiment of the present invention of lithium ionic cell module therein were proposed
Supercapacitor shock-sensitive kinetic model is closer to, therefore is modified on the basis of this module, is realized to super
The simulation calculation of capacitor shock-sensitive characteristic.
The embedded model of lithium ion module is as follows:
But the embedded model only contains electrode stored energy power equation, does not account for the embodiment of the present invention and is proposed
Supercapacitor bombardment by ions sensitlzing effect.
Therefore, the embodiment of the present invention passes through the complex model structure of COMSOL weak form equation and common version partial differential equation
Construction method embeds model to lithium ionic cell module and is modified, so that stored energy power model meets the electrochemistry built
Energy storage-shock-sensitive coupling model system.
On the one hand, embedded model has ignored the influence of the flowing and flow field change of electrolyte to ion concentration field, electric potential field,
It can be edited by the weak form code to embedded equation, realize the amendment to this defect.So-called weak form is limited
Original partial differential equations are carried out a kind of variation treated form in calculating by member.As shown in fig. 6, in COMSOL software systems
" equation view " option is selected in setting, can enter weak form edit pattern.Equation (22) and equation (23) is described
After ion concentration field correction model carries out weak form conversion, the embedded source code in alternative module is achieved that module
It corrects in the flow field of concentration field equation.
On the other hand, in the model system of the embodiment of the present invention relationship in impact acceleration and electrolyte flow field by equation
(20) it describes, can be realized by way of adding new equation in the module with equation (21).The common version that COMSOL is provided
Partial differential equation framework is as follows:
The model equation as shown in equation (20) and equation (21) is compareed, by the corresponding input common version equation of each term coefficient
(25) in, the supplement amendment of emulation module can be completed.
Therefore it can use COMSOL software and supercapacitor shock-sensitive characteristic emulated.Simulation result shows super
Grade capacitor will appear two kinds of typical shock-sensitive phenomenons under different working modes, as shown in Figure 7 respectively.
If supercapacitor immediately begins to discharge after the completion of large current charge, and after discharge is started shortly after by
Acceleration impact, will occur the first sensitivity phenomenon, as shown in Fig. 7 (a).Output voltage fluctuates downwards in impact moment at this time,
It is denoted as Δ V < 0.Δ V indicates the rising value of output voltage in impact process.
If supercapacitor has carried out prolonged self-discharge processes after fully charged, start after self discharge completion
It discharges, is impacted in discharge process, second of sensitivity phenomenon will occur, as shown in Fig. 7 (b).With Fig. 7 (a) on the contrary, this
When output voltage impact moment fluctuate upwards, be denoted as Δ V > 0.
The essence of both sensitivity phenomenons can be preferably explained the emulation of ion concentration field during impact.
For the first case, when supercapacitor carries out large current charge, the rate of kinetic current gain and loss ion is remote
Much larger than the rate of effects of ion diffusion.Therefore, in anode, ion bulk deposition, in cathode, ion is largely consumed.?
Before impact starts, positive ion concentration is much larger than the ion concentration of cathode, the side in ion concentration field distribution such as Fig. 8 (a)
Shown in shape markings.
After impacting generation, the flowing of electrolyte solution rapidly changes ion concentration field distribution, in a very short period of time
Ion concentration distribution in solution is restored to approximate equalization state.This ion redistributes shown in process such as Fig. 8 (a), tsIt represents
The duration of impact.According to the shock-sensitive model of supercapacitor, ion concentration field c1Variation will directly affect electrolysis
Liquid electric potential field Φ1, and then influence its output voltage.
Further, the voltage fluctuation phenomenon that the variation of ion concentration field generates can be solved by following electrochemical principle
It releases.During discharge, ion is constantly combined with anode, and impact is so that ion concentration distribution tends to balanced, namely reduces
The ion of anode.The reduction of positive pole ion is so that supercapacitor positive electrode discharge capacity reduces, to make under its output voltage
Drop.
Second of sensitivity phenomenon in contrast, due to the effect of supercapacitor self discharge effect, experienced for a long time
Self-discharge processes after, ion concentration distribution has become balanced.So being born after capacitor starts heavy-current discharge
The ion concentration of pole starts to be more than significantly anode, as shown in the rectangular markings in Fig. 8 (b).In impact process, ion is dense
Equally restore approximate equalization in a very short period of time in degree field.And the description according to equation (11) to electrolysis liquid phase electric potential field, ion are dense
Spend field c1Influence to electric potential field depends onDue in Fig. 8 (a) and Fig. 8 (b)The symbol of value on the contrary,
So the corresponding voltage fluctuation of second of phenomenon is also fluctuated with the first phenomenon on the contrary, showing as voltage in impact process upwards.
Based on electrolyte ion redistribution effect, impact is so that electrolyte ion distribution of concentration is more balanced, namely increases anode
Ion.Therefore, electrolyte can provide more ions for the faraday's reaction of anode, increase supercapacitor positive electrode
Discharge capacity rises output voltage.
In general, ion concentration distribution when the case where ultracapacitor voltage fluctuates occurs depending on impact.Such as Fig. 7
(a) and shown in Fig. 8 (a), if impact initial time ion concentrates on anode (c1|positive>c1| negative), then it rushes
Voltage will fluctuate downwards during hitting.As shown in Fig. 7 (b) and Fig. 8 (b), on the contrary, if impact initial time ion concentrates on
Cathode (c1|positive<c1| negative), then voltage will fluctuate upwards in the process.
Discharge current and degree of discharge be influence the field distribution of supercapacitor ion concentration two key factors (definition is put
Electric degree is 1 ratio for subtracting output voltage and maximum charging voltage), the emulation mode that the embodiment of the present invention proposes can analyze
Parameter impacts mechanics the influence of lower ion redistribution effect.As shown in figure 9, which show different discharge currents and electric discharge journey
Under degree, the amplitude that the voltage of generation fluctuates upwards is impacted, it is possible thereby to analyze the shock response characteristic of supercapacitor.
Firstly, the degree of discharge of supercapacitor is bigger when discharge current is identical, the voltage for impacting generation fluctuates upwards
Amplitude it is bigger；Secondly, discharge current is bigger when the degree of discharge of supercapacitor is identical, impact the voltage of generation to
The amplitude of upper fluctuation is bigger；Third, when discharge current is smaller, in the relationship such as Fig. 9 of voltage fluctuation amplitude and degree of discharge
Rectangular markings and circle marker line shown in.At this point, voltage fluctuation amplitude and degree of discharge are close when degree of discharge is smaller
Liny sexual intercourse, and when degree of discharge is larger, as degree of discharge continues to increase, the increase of voltage fluctuation amplitude is more and more slow
Slowly, finally tend to restrain.4th, when discharge current is larger, the relationship of voltage fluctuation amplitude and degree of discharge can protect always
Approximately linear is held, as shown in the triangle markings in Fig. 9.
The relationship of supercapacitor surge voltage fluctuation amplitude and discharge current and degree of discharge can be by Figure 10's in Fig. 9
Ion concentration field simulation result is further explained.
Firstly, the generation of ion concentration gradient derives from the accumulation of faraday's reaction electric current gain and loss ionic effect.So putting
Electric degree is bigger, and the ion of cathode accumulation is more, and ion concentration gradient is bigger.Therefore, the ion concentration for impacting generation is equal
Weighing apparatusization redistribution effect is bigger to the change of ion concentration field, and then more significant impact will be also generated to output voltage.
Second, the essence that ion concentration gradient generates is that the rate of faraday's reaction gain and loss ion has been more than ion diffusion
Rate, therefore discharge current is bigger, faraday's reaction is more violent, and ion concentration gradient also will be bigger.
Third, according to ion concentration field kinetic mechanism described in equation (13), the rate of ion diffusion depend on from
The size of sub- concentration gradient, therefore as degree of discharge increases, ion concentration gradient constantly accumulates.When ion concentration gradient accumulates
To it is sufficiently large when, ion diffusion effect will be enough to offset influence of the faraday's reaction to ion concentration field, and then ion concentration field
It is maintained at stable state, as shown in Figure 10.So after degree of discharge is sufficiently large, although degree of discharge continues to increase,
The voltage fluctuation amplitude that impact generates tends towards stability substantially.
Therefore, the emulation mode of the embodiment of the present invention more can comprehensively analyze supercapacitor and impact in mechanics
Under ion concentration redistribution effect.In order to further verify the correctness of simulation analysis conclusion, the embodiment of the present invention utilizes horse
Xie Te hammers experimental system and carries out shock response characteristic test to supercapacitor, and is recorded using CHI660 electrochemical workstation
Voltage responsive signal of the device in impact moment.
Following experiment test confirms the two kinds of shock-sensitive phenomenons discussed in simulation analysis.
Corresponding to the first shock-sensitive phenomenon, experiment test charges to supercapacitor with 20mA electric current, is filling
It immediately begins to discharge and carry out Machete hammering test after the completion of electricity.Shown in device output voltage such as Figure 11 (a) of experimental record,
There is the phenomenon that voltage fluctuates downwards (Δ V < 0) in impact moment.
Corresponding to second of shock-sensitive phenomenon, supercapacitor be full of voltage after it is carried out the holding of long-time constant pressure with
So that its ion concentration field restores balanced, then begin to 20mA current discharge, carries out Machete hammering during discharge and survey
Examination.Shown in device output voltage such as Figure 11 (b) of experimental record, there is voltage in impact moment and fluctuate (Δ V > 0) upwards
Phenomenon.
Therefore, the mechanics proposed according to embodiments of the present invention impacts lower electrolytic solution for super capacitor ion redistribution effect
Emulation mode, it can be achieved that the ion redistribution phenomenon to supercapacitor under mechanics impact effective emulation, simulation result exists
It is qualitative upper consistent with experimental result, the research to supercapacitor mechanics impact characteristics can be effectively facilitated, for applied to Special Force
The supercapacitor research and development for learning environment provide technical support.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be mechanical connect
It connects, is also possible to be electrically connected；It can be directly connected, can also can be in two elements indirectly connected through an intermediary
The interaction relationship of the connection in portion or two elements, unless otherwise restricted clearly.For those of ordinary skill in the art
For, the specific meanings of the above terms in the present invention can be understood according to specific conditions.
In the present invention unless specifically defined or limited otherwise, fisrt feature in the second feature " on " or " down " can be with
It is that the first and second features directly contact or the first and second features pass through intermediary mediate contact.Moreover, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature be directly above or diagonally above the second feature, or be merely representative of
First feature horizontal height is higher than second feature.Fisrt feature can be under the second feature " below ", " below " and " below "
One feature is directly under or diagonally below the second feature, or is merely representative of first feature horizontal height less than second feature.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (9)
1. the emulation mode that a kind of mechanics impacts lower electrolytic solution for super capacitor ion redistribution effect, which is characterized in that including
Following steps:
Establish the stored energy power model of supercapacitor；
In the stored energy power model, insertion mechanics impacts the migration redistribution model of lower electrolyte ion, to constitute base
In energy storage-shock-sensitive coupling model system of supercapacitor；And
Simulation calculation is carried out to the energy storage-shock-sensitive coupling model system using finite element software, to realize that mechanics impacts
Effective emulation of lower electrolytic solution for super capacitor ion redistribution effect.
2. mechanics according to claim 1 impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect,
It is characterized in that, the stored energy power model includes electric double layer effect model and faraday's reaction model.
3. mechanics according to claim 1 impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect,
It is characterized in that, the stored energy power model is the high reversible by occurring between electrode active material and electrolyte material
Redox reaction so that charge occur transfer generate and storage energy, wherein the faraday's reaction model energy storage accounts for master
Lead status.
4. mechanics according to claim 1 impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect,
It is characterized in that, the energy storage-shock-sensitive coupling model system includes the electrode kinetics model of electric double layer effect, faraday
The electrode kinetics model of reaction, the electrolyte ion redistribution mould under ion diffusion model and mechanics impact in electrolyte
Type.
5. the emulation side that mechanics according to claim 1 or 4 impacts lower electrolytic solution for super capacitor ion redistribution effect
Method, which is characterized in that faradic currents amendment is carried out to electric double layer effect model by the stored energy power model, so that institute
Electric potential field of supercapacitor during charging and discharging, ion concentration field are stated in faraday's reaction model and electric double layer effect
Variation tendency under two kinds of mechanism of model drive jointly is determined.
6. mechanics according to claim 1 impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect,
It is characterized in that, electrolyte will be generated directed flow, the power of flow field change by inertia power drive when being embedded in mechanics impact
Process is described by Navier-Stokes equation:
Wherein, u1, ρ1, μ respectively indicates the flow field velocity of electrolyte flow, density, dynamic viscosity.
7. mechanics according to claim 1 impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect,
It is characterized in that, by the complex model construction method of COMSOL weak form equation and common version partial differential equation, to lithium from
Sub- battery module embeds model and is modified, so that the stored energy power model meets the energy storage-shock-sensitive of building
Coupling model system.
8. mechanics according to claim 7 impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect,
It is characterized in that, the common version partial differential equation framework is as follows:
Wherein, u is partial differential equation dependent variable, and t is independent variable, and other parameters are UNIVERSAL COEFFICIENT.
9. mechanics according to claim 1 impacts the emulation mode of lower electrolytic solution for super capacitor ion redistribution effect,
It is characterized in that, being emulated using COMSOL software to the supercapacitor shock-sensitive characteristic, the supercapacitor
Occur two kinds of shock-sensitive phenomenon under different working modes, wherein the first situation be when the supercapacitor into
When row large current charge, the rate of kinetic current gain and loss ion is far longer than the rate of effects of ion diffusion, second situation
With the first described situation conversely, because the self discharge effect of the supercapacitor, ion concentration distribution have become balanced.
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