CN105374571B - Lithium-ion capacitor negative plate and preparation method thereof, winding type lithium ion capacitor - Google Patents
Lithium-ion capacitor negative plate and preparation method thereof, winding type lithium ion capacitor Download PDFInfo
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- CN105374571B CN105374571B CN201410425353.6A CN201410425353A CN105374571B CN 105374571 B CN105374571 B CN 105374571B CN 201410425353 A CN201410425353 A CN 201410425353A CN 105374571 B CN105374571 B CN 105374571B
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Abstract
The invention discloses a kind of lithium-ion capacitor negative plate, including negative current collector, the negative electrode active layer being arranged on negative current collector and the prelithiation layer being arranged on negative electrode active layer, the material of negative electrode active layer include silica-base material and can intercalation/deintercalation lithium ion negative active core-shell material, the material of prelithiation layer includes passivation of lithium powder.In the negative electrode active layer of this lithium-ion capacitor negative plate, silica-base material capacity is big and its pre- embedding lithium after volumetric expansion compensate for prelithiation layer and disappear the space left, during applied to lithium-ion capacitor, battery core will not be caused to loosen, deformation because prelithiation layer after the completion of pre- embedding lithium disappears, so as to reduce the impedance of lithium-ion capacitor, the power density of lithium-ion capacitor is improved, and improves the service life of lithium-ion capacitor.The invention also discloses the preparation method of above-mentioned lithium-ion capacitor negative plate, and the winding type lithium ion capacitor using the lithium-ion capacitor negative plate.
Description
Technical field
The present invention relates to energy storage device field, more particularly to a kind of lithium-ion capacitor negative plate and preparation method thereof,
And the winding type lithium ion capacitor using above-mentioned lithium-ion capacitor negative plate.
Background technology
Lithium-ion capacitor is a kind of positive pole asymmetric capacitor different from negative pole charge-discharge principle, is used in design
The principle of double layer capacitor, constructively employs the negative material of lithium ion battery and the positive pole material of double layer capacitor
The combination of material, while lithium ion is with the addition of in negative pole again, so as to substantially increase the energy density of capacitor.Lithium-ion capacitor
It is a kind of height output, long-life characteristics both with double layer capacitor, while and can provides the new electric power storage of high-energy-density
Component, the useful supplement to existing energy storage device lithium ion battery, ultracapacitor industry is not only, will also be in mixing electricity
The high power domain such as electrical automobile forms part and substituted, and has good market prospects.
As lithium-ion capacitor, there are known to：With by anode electrode and negative electrode across electrolyte can be immersed in
In dividing plate and electrode unit that the electrode laminated body after being laminated forms from its one end winding it is convoluted, have multiple positive poles
And the electrode unit that electrode laminated body of multiple negative poles after the dividing plate that can be impregnated in the electrolytic solution is alternately laminated is formed
Lamination type etc..Presently commercially available winding type lithium ion capacitor, generally include the metal shell of one end open, in housing
Fuse and the sealing-plug using seal casinghousing openend, its type mainly includes wire type (guide pin) and substrate self-supporting (is drawn
Chaff), when to lithium-ion capacitor carry out high current charge-discharge when because both positive and negative polarity guide pin (drawing chaff) be arranged in it is same
Sealing-plug becomes very little so as to cause the restricted cross sectional area of single electrode guide pin (drawing chaff), and both positive and negative polarity guide pin (draws chaff)
It is easy to burn, causes whole lithium-ion capacitor to be scrapped.In order to improve lithium-ion capacitor large current discharging capability, part lithium
Ionistor manufacturer devises a kind of lithium-ion capacitor, and the lithium-ion capacitor includes the metal shell of one end open, should
The openend of metal shell is sealed by metallic sealed cover, and metal shell mutually insulate with metallic sealed cover, makes lithium-ion capacitance
Device anode and cathode terminals are respectively positioned at the one end of housing and the outside of metallic sealed cover, although the lithium-ion capacitor of this kind of structure
Lithium-ion capacitor is solved to a certain extent in heavy-current discharge, the technology that both positive and negative polarity guide pin (drawing chaff) easily burns
Problem, but in seal process, if because of careless manipulation, cause metallic sealed cover to be conducted with metal object, in turn result in lithium
Ionistor short circuit.
In addition, although winding type lithium ion capacitor possesses the advantages of production efficiency is high, but Large Copacity in the market
(being more than 2000F) lithium-ion capacitor mainly uses lamination type, and most important reason is to be difficult to solve the convoluted lithium of Large Copacity
The pre- embedding lithium technique of ionistor negative pole.For pre- embedding lithium, it can assemble using the electrode of pre- embedding lithium as working electrode, use
Lithium metal is the electro-chemical systems to electrode, carries out the doping of electrochemistry, in the method, it is necessary to be taken out from electro-chemical systems pre-
The electrode of embedding lithium, it is binned in battery, capacitor.As the pre-doping method of practicality, use for a long time by making lithium metal
Paper tinsel, which is attached to the electrode containing active material, makes its contact, method after electrolyte is injected by lithium doping in active material.
The technology number of electrodes it is few, using the buckle type electrochemical system of thicker electrode in effectively, but in winding type battery or electric capacity
In device structure, complex procedures or problem be present in the processing of ultrathin lithium band, it is necessary to easy and practical pre-embedding lithium method.
As the method for solving the problem, CN101819880, CN102959662, CN103201803 and CN102301439
In the Wound-type Accumulator proposed, both positive and negative polarity collector is employed with the aluminium foil and copper foil through pore property, then by lithium
Pole is placed in the outer peripheral face or/and inner peripheral surface of the electrode unit, injects electrolyte, now, lithium electrode start to discharge lithium ion and to negative
Pole carries out embedding lithium.In this Wound-type Accumulator, being impregnated with for electrolyte takes long enough, moreover, in order that lithium ion is uniform
Ground, which is embedded in negative pole entirety, to be taken long enough, particularly in the case where manufacturing large-scale winding type lithium ion capacitor, by
Increase the time required to increase winding number, embedding lithium, accordingly, it is difficult to obtain high production efficiency；Further, since both positive and negative polarity collector
Employ with the aluminium foil and copper foil through pore property, should be answered with the not only manufacture craft for the aluminium foil and copper foil for running through pore property
Miscellaneous, production cost is higher, and its electric conductivity is poor, larger using the internal resistance (ESR) of its lithium-ion capacitor produced, greatly
Current charge-discharge electrical property is poor, at the same also in the presence of production on must solve to perforate collector it is electrode coated the problem of.In addition,
The lithium part to be disappeared due to pre- embedding lithium turns into gap, causes and loosens, deforms inside electrode roll core, and to the inside electricity of capacitor
Resistance etc. is had an impact, and such maximization or high capacity lithium-ion capacitor especially are used as into hybrid electric vehicle or electric car etc.
The power supply of automobile, can be for a long time to lithium-ion electric to stronger vibrations that automobile body applies or that automobile body is sent and collision
Container apply, as a result cause its storage performance reduce the problem of.
The content of the invention
Based on this, it is necessary to which the winding type lithium ion capacitor anode piece and its system of pre- embedding lithium can preferably be completed by providing
Preparation Method, and the winding type lithium ion capacitor using above-mentioned lithium-ion capacitor negative plate.
A kind of lithium-ion capacitor negative plate, including negative current collector, the negative pole that is arranged on the negative current collector are lived
Property layer and the prelithiation layer that is arranged on the negative electrode active layer, the material of the negative electrode active layer include silica-base material and can be embedding
Enter/deviate from the negative active core-shell material of lithium ion, the material of the prelithiation layer includes passivation of lithium powder.
In one embodiment, the silica-base material is silicon materials, silicon-nonmetallic composite and silicon-metal composite wood
At least one of material；
The silicon materials are nano silica fume, nano-tube, silicon nanowires or silicon nano thin-film, the nonmetallic composite wood of silicon
Expect for silico-carbo composite, si-glass composite, silicon-ceramic composite, silicon-conducting polymer composite material or silica
Compound, silicon-metal composite are Mg2Si、NiSi、FeSi、FeSi2, TiSi or Cu5Si。
In one embodiment, the negative active core-shell material is soft carbon, hard carbon, carbonaceous mesophase spherules, polyacene and polyphenyl
At least one of amine.
In one embodiment, the material of the negative electrode active layer also includes 0 part~8 parts of conductive agent according to mass fraction
With 2 parts~10 parts of binding agent, the thickness of the negative electrode active layer is 40 μm~100 μm.
In one embodiment, the passivation of lithium powder is core shell structure, and the core of the passivation of lithium powder is lithium powder, the passivation
The shell of lithium powder is the inorganic lithium salt for being insoluble in water.
In one embodiment, the inorganic lithium salt is Li2CO3、Li3PO4, LiF and LiAlO2At least one of.
In one embodiment, the prelithiation layer according to mass fraction include 40 parts~60 parts the passivation of lithium powder and
2 parts~10 parts of binding agent, the thickness of the prelithiation layer is 2 μm~12 μm.
A kind of preparation method of above-mentioned lithium-ion capacitor negative plate, comprises the following steps：
Negative electrode active slurry is coated with the negative current collector and forms negative electrode active pulp layer, roll-in after drying is described
Negative electrode active pulp layer forms negative electrode active layer, and the material of the negative electrode active slurry includes silica-base material and can intercalation/deintercalation
The negative active core-shell material of lithium ion；And
Spraying or sputter prelithiation slurry form prelithiation pulp layer, roll-in after drying, institute on the negative electrode active layer
State prelithiation pulp layer and form prelithiation layer, obtain the negative plate, the material of the prelithiation slurry includes passivation of lithium powder.
A kind of winding type lithium ion capacitor, including convoluted battery core, electrolyte and capacitor casing；It is described convoluted
Battery core winds after being stacked gradually by positive plate, barrier film and negative plate and formed, and the negative plate is that above-mentioned lithium-ion capacitor is born
Pole piece, the convoluted battery core and the electrolyte are placed in the capacitor protector body；
The positive plate exceeds the barrier film and the negative plate in one end of the convoluted battery core, and the negative plate exists
The other end of the convoluted battery core exceeds the barrier film and the positive plate.
This lithium-ion capacitor negative plate includes negative current collector, negative electrode active layer and prelithiation layer, negative electrode active layer
Material include silica-base material and can intercalation/deintercalation lithium ion negative active core-shell material, silica-base material capacity is big and its pre- embedding lithium
Volumetric expansion afterwards compensate for the space that the disappearance of prelithiation layer leaves.
, will not be because of prelithiation after the completion of pre- embedding lithium when this lithium-ion capacitor negative plate is applied to lithium-ion capacitor
Layer disappears and causes battery core to loosen, deformation, can preferably complete pre- embedding lithium, while reduces the impedance of lithium-ion capacitor,
The power density of lithium-ion capacitor is improved, and improves the service life of lithium-ion capacitor.
Brief description of the drawings
Fig. 1 is the flow chart of the lithium-ion capacitor negative pole piece preparation method of an embodiment；
Fig. 2 is the structural representation of the winding type lithium ion capacitor of an embodiment；
Fig. 3 is the battery core expanded schematic diagram of winding type lithium ion capacitor as shown in Figure 2；
Fig. 4 is the rate discharge curves figure of winding type lithium ion capacitor made from embodiment 1；
Fig. 5 is the normal temperature 10C cycle performances of winding type lithium ion capacitor made from embodiment 1.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, below in conjunction with the accompanying drawings to the present invention
Embodiment be described in detail.Many details are elaborated in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case of running counter to intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
One embodiment lithium-ion capacitor negative plate, including negative current collector, the negative pole that is arranged on negative current collector
Active layer and the prelithiation layer being arranged on negative electrode active layer.
The material of negative electrode active layer include silica-base material and can intercalation/deintercalation lithium ion negative active core-shell material, prelithiation
The material of layer includes passivation of lithium powder.
Negative current collector can be copper foil.
Silica-base material is at least one of silicon materials, silicon-nonmetallic composite and silicon metallic composite.
Silicon materials are nano silica fume, nano-tube, silicon nanowires, silicon nano thin-film etc..
Silicon nonmetallic composite is silico-carbo composite, si-glass composite, silicon-ceramic composite, silicon-are led
Electric polymer composite, Si oxide (SiOx) etc..
Silicon-metal composite is Mg2Si、NiSi、FeSi、FeSi2、TiSi、Cu5Si etc..
Negative active core-shell material can be at least one of soft carbon, hard carbon, carbonaceous mesophase spherules, polyacene and polyaniline.
Hard carbon refers to not graphitisable indefinite form carbon, and soft carbon refers to graphitisable indefinite form carbon.
Negative electrode active layer includes 5 parts~20 parts of silica-base material and 70 parts~90 parts of negative electrode active material according to mass fraction
Material.
In present embodiment, negative electrode active layer also includes 0 part~8 parts of conductive agent and 2 parts~10 according to mass percent
The binding agent of part.
Conductive agent can be at least one of conductive carbon black, electrically conductive graphite, Nano carbon fibers peacekeeping CNT.
Binding agent can be polyvinylidene fluoride, ethylene propylene diene terpolymers, ethylene acrylic, ethylene vinyl acetate
Vinyl acetate and at least one of butadiene-styrene rubber and carboxymethyl cellulose.
In present embodiment, the thickness of negative electrode active layer can be 40 μm~100 μm.
Passivation of lithium powder is core shell structure, and the core of passivation of lithium powder is lithium powder, and the shell of passivation of lithium powder is the inorganic lithium for being insoluble in water
Salt.
Passivation of lithium powder can be directly commercially available.
The mass percent that lithium powder accounts for passivation of lithium powder is 85%~95%.
Inorganic lithium salt is Li2CO3、Li3PO4, LiF and LiAlO2At least one of.
Prelithiation layer includes 40 parts~60 parts of passivation of lithium powder and 2 parts~10 parts of binding agent according to mass fraction.Pre- lithium
The thickness for changing layer is 2 μm~12 μm.
Binding agent can be polyvinylidene fluoride, ethylene propylene diene terpolymers, ethylene acrylic, ethylene vinyl acetate second
At least one of alkene ester and butadiene-styrene rubber.
This lithium-ion capacitor negative plate includes negative current collector, negative electrode active layer and prelithiation layer, negative electrode active layer
Material include silica-base material and can intercalation/deintercalation lithium ion negative active core-shell material, silica-base material capacity is big and its pre- embedding lithium
Volumetric expansion afterwards compensate for the space that the disappearance of prelithiation layer leaves.
, will not be because of prelithiation after the completion of pre- embedding lithium when this lithium-ion capacitor negative plate is applied to lithium-ion capacitor
Layer disappears and causes battery core to loosen, deformation, can preferably complete pre- embedding lithium, while reduces the impedance of lithium-ion capacitor,
The power density of lithium-ion capacitor is improved, and improves the service life of lithium-ion capacitor.
The preparation method of the lithium-ion capacitor negative plate of an embodiment as shown in Figure 1, comprises the following steps：
S10, negative electrode active slurry formation negative electrode active pulp layer, roll-in after drying, negative pole are coated with negative current collector
Active slurry layer forms negative electrode active layer.
The material of negative electrode active slurry include silica-base material and can intercalation/deintercalation lithium ion negative active core-shell material.
Negative current collector is copper foil.
Silica-base material is at least one of silicon materials, silicon-nonmetallic composite and silicon metallic composite.
Silicon materials are nano silica fume, nano-tube, silicon nanowires, silicon nano thin-film etc..
Silicon nonmetallic composite is silico-carbo composite, si-glass composite, silicon-ceramic composite, silicon-are led
Electric polymer composite, Si oxide (SiOx) etc..
Silicon-metal composite is Mg2Si、NiSi、FeSi、FeSi2、TiSi、Cu5Si etc..
Negative active core-shell material can be at least one of soft carbon, hard carbon, carbonaceous mesophase spherules, polyacene and polyaniline.
Negative electrode active layer includes 5 parts~20 parts of silica-base material and 70 parts~90 parts of negative electrode active material according to mass fraction
Material.
In present embodiment, negative electrode active layer also includes 0 part~8 parts of conductive agent and 2 parts~10 according to mass percent
The binding agent of part.
Specifically, negative electrode active slurry is obtained by following operative configuration：According to mass percent, by 5 parts~20 parts
Silica-base material, 70 parts~90 parts of negative active core-shell material, 0 part~8 parts of conductive agent and 2 parts~10 parts of binding agent and solvent mix
Negative electrode active slurry is obtained after even.
Conductive agent can be at least one of conductive carbon black, electrically conductive graphite, Nano carbon fibers peacekeeping CNT.
Binding agent can be polyvinylidene fluoride, ethylene propylene diene terpolymers, ethylene acrylic, ethylene vinyl acetate
At least one of vinyl acetate, butadiene-styrene rubber and carboxymethyl cellulose.
Solvent can be water, aliphatic hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbons, symmetrical ether, asymmetrical ether, cyclic ethers and tetrahydrofuran at least
It is a kind of.
In present embodiment, the thickness of negative electrode active layer can be 40 μm~100 μm.
S20, spraying or sputter prelithiation slurry form prelithiation pulp layer, drying on the negative electrode active layer that S10 is obtained
Roll-in afterwards, prelithiation pulp layer form prelithiation layer, obtain the negative plate.
The material of prelithiation slurry includes passivation of lithium powder.
Passivation of lithium powder is core shell structure, and the core of passivation of lithium powder is lithium powder, and the shell of passivation of lithium powder is the inorganic lithium for being insoluble in water
Salt.
The mass percent that lithium powder accounts for passivation of lithium powder is 85%~95%.
Inorganic lithium salt is Li2CO3、Li3PO4, LiF and LiAlO2At least one of.
Prelithiation layer includes 40 parts~60 parts of passivation of lithium powder and 2 parts~10 parts of binding agent according to mass fraction.
Specifically, prelithiation slurry is obtained by following operative configuration：It is blunt by 40 parts~60 parts according to mass percent
Prelithiation slurry is obtained after changing lithium powder and 2 parts~10 parts of binding agent and the mixing of 38 parts~50 parts of organic solvent.
Binding agent can be polyvinylidene fluoride, ethylene propylene diene terpolymers, ethylene acrylic, ethylene vinyl acetate second
At least one of alkene ester and butadiene-styrene rubber.
Organic solvent can be aliphatic hydrocarbon, cyclic hydrocarbon, aromatic hydrocarbons, symmetrical ether, asymmetrical ether, cyclic ethers and tetrahydrofuran at least
It is a kind of.
The thickness of prelithiation layer can be 2 μm~12 μm.
Lithium-ion capacitor negative plate made from the preparation method of this lithium-ion capacitor negative plate includes stacking gradually
Negative current collector, negative electrode active layer and prelithiation layer, the material of negative electrode active layer includes silica-base material and can intercalation/deintercalation lithium
The negative active core-shell material of ion, silica-base material capacity is big and its pre- embedding lithium after volumetric expansion compensate for prelithiation layer and disappear to leave
Space.
, will not be because of pre- lithium after the completion of pre- embedding lithium when obtained lithium-ion capacitor negative plate is applied to lithium-ion capacitor
Change layer to disappear and cause battery core to loosen, deformation, can preferably complete pre- embedding lithium, while reduce the resistance of lithium-ion capacitor
It is anti-, the power density of lithium-ion capacitor is improved, and improve the service life of lithium-ion capacitor.
The preparation method simple production process of this lithium-ion capacitor negative plate, cost is low, possesses practical application foreground.
Above-mentioned lithium-ion capacitor negative plate can apply to a variety of lithium-ion capacitors, below with its application with it is convoluted
It is introduced exemplified by lithium-ion capacitor.
The winding type lithium ion capacitor of an embodiment as shown in Figures 2 and 3, including convoluted battery core 10, electrolysis
Liquid and capacitor case 20.
Convoluted battery core 10 and electrolyte are placed in capacitor case 20.
Convoluted battery core 10 is wound after being stacked gradually by positive plate 12, barrier film 14 and negative plate 16 and formed, and negative plate 16 is adopted
With above-mentioned lithium-ion capacitor negative plate.
With reference to Fig. 3, positive plate 12 exceeds barrier film 14 and negative plate 16 in one end of convoluted battery core 10, and negative plate 16 is being rolled up
The other end of geometric pattern battery core 10 exceeds barrier film 14 and positive plate 12.
This design so that positive plate 12 and negative plate 16 stretch out at the both ends of convoluted battery core 10 respectively, will be convoluted
Battery core 10 is placed in capacitor case 20, positive plate 12 and negative plate 16 by the part each stretched out respectively with capacitor case
20 both ends electrical connection.Avoid traditional electrical connection that battery core and capacitor case are completed by electrode guide pin (drawing chaff)
Lithium-ion capacitor, when carrying out high current charge-discharge to lithium-ion capacitor, because both positive and negative polarity guide pin (drawing chaff) is worn
Become very little in same sealing-plug so as to cause the restricted cross sectional area of single electrode guide pin (drawing chaff), both positive and negative polarity guide pin
(drawing chaff) is easy to burn, and causes whole lithium-ion capacitor to be scrapped.
Positive plate 12 includes plus plate current-collecting body and the positive-active layer being arranged on plus plate current-collecting body.
Plus plate current-collecting body is aluminium foil.
The material of positive-active layer can be that mass ratio is 70~88：5~10：2~12 activated carbon, conductive agent and bonding
The mixture of agent.
In present embodiment, positive plate 12 is not provided with positive-active layer beyond the part of barrier film 14 and negative plate 16.
Similar, negative plate 16 is not provided with negative electrode active layer beyond the part of barrier film 14 and positive plate 12.
The negative plate 16 of this lithium-ion capacitor including the negative current collector, negative electrode active layer and pre- lithium that stack gradually
Change layer, the material of negative electrode active layer include silica-base material and can intercalation/deintercalation lithium ion negative active core-shell material, silica-base material holds
Amount is greatly and the volumetric expansion after its pre- embedding lithium compensate for the space that the disappearance of prelithiation layer leaves.
, will not be because of pre- lithium after the completion of pre- embedding lithium when obtained lithium-ion capacitor negative plate is applied to lithium-ion capacitor
Change layer to disappear and cause battery core to loosen, deformation, so as to reduce the impedance of lithium-ion capacitor, improve lithium-ion capacitor
Power density, and improve the service life of lithium-ion capacitor.
It is specific embodiment below.
Embodiment 1
Prepare model：φ 65*155 winding type lithium ion capacitor, battery core are takeup type, pass through the appearance of bottomed tube
Device and cover encapsulation.
Negative active core-shell material selection soft carbon, silica-base material selection silico-carbo composite, soft carbon and silico-carbo composite
Physical and chemical indexes see the table below 1.
| Project | D50 | Si | Density | Specific surface area | Capacity first | Efficiency first |
| Unit | μm | nm | g/cm3 | m2/g | mAh/g | % |
| Soft carbon | 10-13 | 0.9-1.2 | <2.3 | ≥250 | ≥80 | |
| Silicon/carbon | 19-23 | 100-200 | 0.9-1.1 | 1.5-5.0 | ≥500 | ≥85 |
Table 1：The physical and chemical indexes of soft carbon and silico-carbo composite.
In the present embodiment, silico-carbo composite is purchased from Bei Terui companies, and article No. (or specification) is：BTR Si/C-II.
Positive-active layer is shown in Table 2 with the physical and chemical indexes of activated carbon.
Table 2：The physical and chemical indexes of activated carbon.
The preparation of prelithiation slurry：By passivation of lithium powder, tetrahydrofuran and polyvinylidene fluoride in mass ratio 52：42：6 mixing
Stir, obtain prelithiation slurry.In the present embodiment, passivation of lithium powder is purchased from FMC Lihium companies, and article No. (or specification) is
The preparation of lithium-ion capacitor cathode pole piece：By 89wt% soft carbons, 5wt%Si-C, 2wt% conductive agents (Super
P), 1.5wt% carboxymethyl celluloses, 2.5wt% butadiene-styrene rubber are mixed into slurry with water, active material slurry are made, using painting
Cloth machine is coated on copper foil and dried at 120 DEG C, and coating thickness is 250 μm, and it is 70 μm to dry the thickness after compacting, then through roller
After pressure, the prelithiation slurry of above-mentioned preparation is coated with using coating machine, coating thickness is controlled at 10 μm, is dried the thickness after compacting and is
2 μm, roll-in after being dried at 120 DEG C, then carry out trimming, cut-parts, slitting and winding.
Anode pole piece is prepared in accordance with the following methods：Activated carbon (is lived used by using super capacitor electrode slice is made
Property charcoal) with conductive agent SuperP, polyfluortetraethylene of binding element (PTFE) in mass ratio 90：5：5 are made slurry, are coated on aluminium foil
And dried at 120 DEG C, coating thickness is 230 μm, and it is 90 μm to dry the thickness after compacting, through roll-in, trimming, cut-parts, slitting
And winding.
The making of lithium-ion capacitor：Cathode pole piece, anode pole piece and the membrane winding that above-mentioned making is obtained are into section
For gyrate fuse, positive pole and negative pole are configured to respective uncoated portion and are not projected into outside than barrier film in the opposite direction
Side.φ 65*155 cylindric lithium-ion capacitor is made, (solute of electrolyte is LiPF6 to injection electrolyte, and solvent is carbonic acid
Vinyl acetate and diethyl carbonate) 6 hours are stood afterwards, 3.3V chemical conversions, welding closing shaping after exhaust.
Embodiment 2
The performance test of winding type lithium ion capacitor made from embodiment 1.
Obtained winding type lithium ion capacitor is subjected to multiplying power discharging property test at normal temperatures, high rate performance has been tested
Cheng Hou, 10C charge and discharge cycles tests are carried out to lithium-ion capacitor.
Multiplying power discharging property method of testing is：Obtained winding type lithium ion capacitor is filled into 10C according to 10C at normal temperatures
Put 5 weeks, 10C, which fills 50C, to be put 5 weeks, and 10C, which fills 100C, to be put 5 weeks, and 10C, which fills 150C, to be put 5 weeks, and 10C, which fills 200C, to be put 5 weeks, and obtained multiplying power is put
Electric curve is as shown in Figure 4.
As seen from Figure 4, winding type lithium ion capacitor, 50C/10C, 100C/10C, 150C/ made from embodiment 1
The conservation rate of 10C, 200C/10C discharge capacity is 88.2%, 81.6%, 78.9%, 73.4%.
Normal temperature 10C cycle charge-discharge conditions are：10C constant-current charges to voltage is 4.0V, is stood several minutes, 4.0V constant pressures are filled
Electricity to electric current is 0.2C, is stood several minutes, and 10C constant-current discharges to voltage are 2.0V, is stood several minutes.Its cycle life curve is such as
Shown in Fig. 5.
As seen from Figure 5, after winding type lithium ion capacitor charging/discharging made from embodiment 1 circulates 5000 times, it holds
Measure conservation rate and be more than 90%.
To sum up, by setting negative electrode active layer in negative current collector, prelithiation nitride layer then is set in negative electrode active layer, it is real
Apply winding type lithium ion capacitor made from example 1 and disclosure satisfy that the lithium-ion capacitor characteristic to be reached, and its internal resistance is relatively low,
Cycle efficieny is high.
In addition, this winding type lithium ion capacitor processing technology is simple, process conditions are more prone to control.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of lithium-ion capacitor negative plate, the lithium-ion capacitor negative plate is used for winding type lithium ion capacitor, its
It is characterised by, including negative current collector, the negative electrode active layer that is arranged on the negative current collector and is arranged on the negative pole and lives
Property layer on prelithiation layer, the material of the negative electrode active layer include silica-base material and can the negative pole of intercalation/deintercalation lithium ion live
Property material, the material of the prelithiation layer include passivation of lithium powder；
The negative electrode active layer includes 5 parts~20 parts of the silica-base material according to mass fraction and 70 parts~90 parts described is born
Pole active material.
2. lithium-ion capacitor negative plate according to claim 1, it is characterised in that the silica-base material be silicon materials,
At least one of silicon-nonmetallic composite and silicon-metal composite；
The silicon materials are nano silica fume, nano-tube, silicon nanowires or silicon nano thin-film, and the silicon nonmetallic composite is
Silico-carbo composite, si-glass composite, silicon-ceramic composite, silicon-conducting polymer composite material or silicon oxidation
Thing, the silicon-metal composite are Mg2Si、NiSi、FeSi、FeSi2, TiSi or Cu5Si。
3. lithium-ion capacitor negative plate according to claim 1, it is characterised in that the negative active core-shell material is soft
At least one of carbon, hard carbon, carbonaceous mesophase spherules, polyacene and polyaniline.
4. lithium-ion capacitor negative plate according to claim 1, it is characterised in that the material of the negative electrode active layer is pressed
Also include 0 part~8 parts of conductive agent and 2 parts~10 parts of binding agent according to mass fraction, the thickness of the negative electrode active layer is 40 μ
M~100 μm.
5. lithium-ion capacitor negative plate according to claim 1, it is characterised in that the passivation of lithium powder is nucleocapsid knot
Structure, the core of the passivation of lithium powder is lithium powder, and the shell of the passivation of lithium powder is the inorganic lithium salt for being insoluble in water.
6. lithium-ion capacitor negative plate according to claim 5, it is characterised in that the inorganic lithium salt is Li2CO3、
Li3PO4, LiF and LiAlO2At least one of.
7. according to the lithium-ion capacitor negative plate described in claim 1,5 or 6, it is characterised in that the prelithiation layer according to
Mass fraction includes 40 parts~60 parts of the passivation of lithium powder and 2 parts~10 parts of binding agent, and the thickness of the prelithiation layer is 2
μm~12 μm.
8. a kind of preparation method according to lithium-ion capacitor negative plate according to any one of claims 1 to 7, its feature exists
In comprising the following steps：
Negative electrode active slurry is coated with the negative current collector and forms negative electrode active pulp layer, roll-in after drying, the negative pole
Active slurry layer forms negative electrode active layer, the material of the negative electrode active slurry include silica-base material and can intercalation/deintercalation lithium from
The negative active core-shell material of son；And
Spraying or sputter prelithiation slurry form prelithiation pulp layer on the negative electrode active layer, and roll-in after drying is described pre-
Lithiumation pulp layer forms prelithiation layer, obtains the negative plate, the material of the prelithiation slurry includes passivation of lithium powder.
9. a kind of winding type lithium ion capacitor, it is characterised in that including convoluted battery core, electrolyte and capacitor casing；
The convoluted battery core winds after being stacked gradually by positive plate, barrier film and negative plate and formed, and the negative plate is will according to right
The lithium-ion capacitor negative plate any one of 1~7 is sought, the convoluted battery core and the electrolyte are placed in described
In capacitor protector body；
The positive plate exceeds the barrier film and the negative plate in one end of the convoluted battery core, and the negative plate is described
The other end of convoluted battery core exceeds the barrier film and the positive plate.
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| CN108428564A (en) * | 2017-02-14 | 2018-08-21 | 东莞东阳光科研发有限公司 | A kind of preparation method of lithium-ion capacitor negative plate |
| CN107248451B (en) * | 2017-07-28 | 2019-01-11 | 中国科学院电工研究所 | A kind of lithium-ion capacitor of high-energy density |
| KR102283684B1 (en) | 2017-07-31 | 2021-08-02 | 주식회사 엘지에너지솔루션 | Lithium deposited anode for Lithium Second Battery and Method for Preparation thereof |
| CN108493392A (en) * | 2018-01-26 | 2018-09-04 | 南昌大学 | A kind of method of Li-Si alloy surface fluorination |
| CN109713215B (en) * | 2018-12-25 | 2022-03-11 | 深圳市倍特力电池有限公司 | Lithium-supplement negative plate, preparation method thereof and lithium ion battery |
| CN110428983B (en) * | 2019-08-22 | 2021-07-16 | 杭州求实新材料科技有限公司 | Pre-sodium treatment method for MXene electrode material of sodium ion capacitor |
| KR20210056169A (en) * | 2019-11-08 | 2021-05-18 | 주식회사 엘지화학 | Negative electrode, method for preparing the negative electrode, and secondary battery including the negative electrode |
| WO2021174443A1 (en) * | 2020-03-04 | 2021-09-10 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
| CN114094111B (en) * | 2020-07-31 | 2024-01-09 | 比亚迪股份有限公司 | Lithium supplementing current collector, preparation method of lithium supplementing current collector, negative electrode and lithium ion battery |
| CN112436194B (en) * | 2020-11-30 | 2022-05-24 | 蜂巢能源科技有限公司 | Method for supplementing lithium to lithium ion battery through anode |
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