CN209200066U - Composite negative plate, secondary cell - Google Patents
Composite negative plate, secondary cell Download PDFInfo
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- CN209200066U CN209200066U CN201822080185.8U CN201822080185U CN209200066U CN 209200066 U CN209200066 U CN 209200066U CN 201822080185 U CN201822080185 U CN 201822080185U CN 209200066 U CN209200066 U CN 209200066U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The utility model provides a kind of composite negative plate, the composite negative plate includes the metal foil as negative current collector and negative electrode active material simultaneously, the solid electrolyte film layer on one surface of metal foil, and the DLC film layer being arranged in the solid electrolyte film layer away from the surface of the metal foil are set.The solid-state electrolyte layer, which has, preferably leads lithium performance, improves composite metal negative pole/electrolyte interface ion diffusion rates, improves battery high rate performance；And the solid-state electrolyte layer can be effectively isolated contact of the composition metal surface with electrolyte, reduce side reaction process, improve battery coulombic efficiency；And the solid-state electrolyte layer can also provide effective mechanical protection to composite metal negative pole and act on, and improve composite metal negative pole in electrochemical reaction process because of pulverizing problem caused by volume change, to effectively improve cycle performance of battery.
Description
Technical field
The utility model belongs to battery cathode technical field more particularly to a kind of composite negative plate, a kind of secondary cell.
Background technique
Currently used lithium ion battery manufacturing cost is higher, and battery is discarded to will cause serious environmental problem.Especially
All there is the challenge of cost and course continuation mileage in the power battery of new-energy automobile.And Tang Yong Ping team utility model is a kind of new
Type high-energy density aluminium-graphite Dual-ion cell technology can manufacture efficient, low completely new energy-storage battery.This novel battery
The positive and negative anodes of conventional lithium ion battery are adjusted, with graphite substitution that is cheap and being easy to get at present batch application in lithium from
Positive electrode of cobalt acid lithium, LiMn2O4, ternary or the LiFePO4 of sub- battery as battery；It is negative as battery simultaneously using aluminium foil
Pole material and negative current collector；Electrolyte is made of conventional lithium salts and carbonate based organic solvent (about aluminium in Dual-ion cell
The particular technique content of cathode protection, referring to the Chinese utility model patent of such as Tang Yong Ping et al., CN201711439546.7).
The battery working principle is different from conventional lithium ion battery, and in charging process, anion intercalated reaction occurs for positive graphite, and aluminium
Aluminum-copper-lithium alloysization reaction occurs for cathode, and discharge process is then opposite.This novel reaction mechanism not only significantly improves the work of battery
Make voltage (3.8V-4.6V), while the quality, volume and manufacturing cost of battery is greatly reduced, thus General Promotion full battery
Energy density.
However, this novel metal-graphite Dual-ion cell metal negative electrode occur aluminum-copper-lithium alloysization reaction when, due to
The growth of lithium Zhi Jing leads to the expansion of volume, and aluminum honeycomb can crush rupture, substantially reduce the cycle performance of battery.
Utility model content
The purpose of this utility model is to provide a kind of composite negative plate, a kind of secondary cell, it is intended to solve existing double
When metal-lithium alloyage reaction occurs for the metal negative electrode of ion battery, metal negative electrode is easy to crush rupture, leads to circulating battery
The problem of capable of reducing.
To realize that above-mentioned purpose of utility model, the technical solution adopted in the utility model are as follows:
The utility model first aspect provides a kind of composite negative plate, and the composite negative plate includes while being used as cathode collection
The solid electrolyte film layer on one surface of metal foil is arranged in the metal foil of fluid and negative electrode active material, and in institute
State the DLC film layer that solid electrolyte film layer is arranged away from the surface of the metal foil.
Preferably, the composite negative plate is by the metal foil, the solid electrolyte film layer and the diamond-like
Film layer composition, and the metal foil is substrate, the solid electrolyte film layer is middle layer, the DLC film layer
For outermost layer.
Preferably, the metal foil is selected from aluminium foil, copper foil, iron foil, tinfoil paper, silver foil, goldleaf, platinum foil, zinc foil, lead foil, nickel
One or more of foil.
Preferably, the solid electrolyte film layer choosing from lithium phosphine oxygen nitrogen layer, polypropylene nitrile layer, polyvinylidene fluoride layer,
One or more of polyoxyethylene layer, silicone layer, sulfide electrolyte layer.
Preferably, the metal foil with a thickness of 20~150 μm.
Preferably, the metal foil with a thickness of 40~60 μm.
Preferably, the solid electrolyte film layer with a thickness of 20~300nm.
Preferably, the solid electrolyte film layer with a thickness of 80~120nm.
Preferably, the layer of the DLC film is with a thickness of 10~50nm.
Preferably, the layer of the DLC film is with a thickness of 15~20nm.
And the utility model second aspect provides a kind of secondary cell, including anode, cathode, is arranged in the anode
Diaphragm between the cathode, wherein the cathode is composite negative plate described in the utility model.
Composite negative plate provided by the utility model, the at the same time metal foil as negative current collector and negative electrode active material
Surface sets gradually solid electrolyte film layer and DLC film layer.Wherein, the solid-state electrolyte layer has preferable
Lithium performance is led, can be improved composite metal negative pole/electrolyte interface ion diffusion rates, improves battery high rate performance；And it is described
Solid-state electrolyte layer can be effectively isolated contact of the composition metal surface with electrolyte, reduce side reaction process, improve battery
Coulombic efficiency；And the solid-state electrolyte layer can also provide effective mechanical protection to composite metal negative pole and act on, and improve multiple
Metal negative electrode is closed in electrochemical reaction process because of pulverizing problem caused by volume change, to effectively improve circulating battery
Energy.Based on this, DLC film layer, Ke Yitong are set away from the surface of the metal foil in the solid electrolyte film layer
Cross influence of the DLC film layer isolation water oxygen infiltration to solid electrolyte film layer, it is ensured that the solid electrolyte film layer
Give full play to its function；Meanwhile DLC film layer has the advantages that high rigidity, thus under conditions of relatively thin, Ke Yishi
Now to the protection of solid electrolyte film layer, and then it is preferably wilful to assign clad aluminum negative electrode tab, and avoids to ionic conductivity
Influence.
Secondary cell provided by the utility model, cathode are above-mentioned composite negative plate, since the cathode has preferably
Stability, it is thus possible to improve the cycle performance of secondary cell.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of composite negative plate provided by the embodiment of the utility model；
Fig. 2 is magnetic-controlled sputtering coating equipment schematic diagram provided by the embodiment of the utility model；
When Fig. 3 is that magnetron sputtering provided by the embodiment of the utility model prepares LiPON layer, target power output and deposition rate
Relational graph between effect, ionic conductivity；
When Fig. 4 is that magnetron sputtering provided by the embodiment of the utility model prepares LiPON layer, target power output and deposition rate
Relational graph between effect, ionic conductivity；
When Fig. 5 is that magnetron sputtering provided by the embodiment of the utility model prepares LiPON layer, lithium phosphate target and the aluminium
Relational graph between the distance between foil and ionic conductivity；
Fig. 6 is the cell voltage and curve of double curvature figure that the utility model embodiment 1 provides；
Fig. 7 is the battery high rate performance curve graph that the utility model embodiment 1 provides；
Fig. 8 is the cycle performance of battery figure that the utility model embodiment 1 provides.
Specific embodiment
In order to which the technical problems to be solved in the utility model, technical solution and beneficial effect is more clearly understood, below
In conjunction with the embodiments, the present invention will be further described in detail.It should be appreciated that specific embodiment described herein is only
To explain the utility model, it is not used to limit the utility model.
In the description of the present invention, it should be understood that term " first ", " second " are used for description purposes only, and
It cannot be understood as indicating or implying relative importance or implicitly indicate the quantity of indicated technical characteristic.It defines as a result,
The feature of " first ", " second " can explicitly or implicitly include one or more of the features.In the utility model
In description, the meaning of " plurality " is two or more, unless otherwise specifically defined.
In conjunction with Fig. 1, on the one hand the utility model embodiment provides a kind of composite negative plate, and the composite negative plate includes same
The solid electrolyte film layer on 10 1 surface of aluminium foil is arranged in the metal foil 10 of Shi Zuowei negative current collector and negative electrode active material
20, and solid electrolyte film layer 20 is set away from the DLC film layer 30 on the surface of metal foil 10.
The composite negative plate includes three-decker, specifically, including aluminium foil 10, the lamination on 10 1 surface of aluminium foil is arranged in
Structure, the laminated construction include the solid electrolyte film layer 20 for being directly incorporated in 10 surface of aluminium foil, and are arranged in solid-state
DLC film layer 30 of the electrolyte thin film layer 20 away from the surface of aluminium foil 10.It is described as a particular preferred embodiment
Composite negative plate is made of metal foil 10, solid electrolyte film layer 20 and DLC film layer 30, and metal foil 10 is base
Bottom, solid electrolyte film layer 20 are middle layer, DLC film layer 30 is outermost layer.
Each layer is described in detail below.
Metal foil 10
In the utility model embodiment, metal foil 10 is used as negative current collector and negative electrode active material, i.e., the described gold simultaneously
When belonging to foil 10 as battery cathode, do not need to re-form other negative electrode active materials in metal foil 10.
In some embodiments, metal foil 10 is selected from aluminium foil, copper foil, iron foil, tinfoil paper, silver foil, goldleaf, platinum foil, zinc foil, lead
One or more of foil, nickel foil.The metal foil enumerated can be simultaneously as the negative current collector of battery and negative electrode active material
Material uses.
Metal foil 10 with a thickness of 20 microns~150 microns, to meet it while be used as negative current collector and cathode living
The requirement of property material.In a preferred embodiment, metal foil 10 with a thickness of 40 microns~60 microns.Most preferred embodiment the most,
Metal foil 10 with a thickness of 50 microns.
Solid electrolyte film layer 20
When metal foil 10 is especially aluminium foil as cathode, volume expansion occurs during with lithium ion alloying, makes
Cause battery capacity to decay at electrode dusting, reduces circulating battery stability.The utility model embodiment is thin by solid electrolyte
Film layer 20 is formed in metal foil 10, covers 10 surface of metal foil, forms protective layer.Solid electrolyte material, which has, preferably leads
Lithium performance, and the metal foil 10 can be subjected to sealing as protective layer.
In some embodiments, the solid electrolyte film layer choosing from lithium phosphine oxygen nitrogen layer, polypropylene nitrile layer, gather inclined difluoro
One or more of pvdf layer, polyoxyethylene layer, silicone layer, sulfide electrolyte layer.Above-mentioned solid electrolyte is thin
Film layer, which not only has, preferably leads lithium performance, and can effective sealing metal foil 1, avoid metal negative electrode from crushing rupture and take off
From.
As particular preferred embodiment, the solid electrolyte film layer is lithium phosphine oxygen nitrogen layer.LiPON material itself
With preferably lithium performance is led, the conductivity of lithium ion when battery work will not influence；Meanwhile solid electrolyte film layer is made
The metal foil 10 is subjected to sealing for protective layer material, metal-lithium alloyage reaction especially aluminum-copper-lithium alloysization can be inhibited anti-
Dusting during 10 volume expansion of seasonable metal foil, avoids cathode from crushing rupture and be detached from, and improves battery coulombic efficiency, reduces
Irreversible capacity improves the cyclical stability of battery.In the utility model embodiment, the thickness of solid electrolyte film layer 20 is set
It sets, that the metal foil 10 can be carried out sealing, prevents as battery cathode (while as negative current collector and negative electrode active
Material) 10 dusting of metal foil be advisable, it is too thin then small to the protective effect of then metal foil 10, said effect cannot be played.But to the greatest extent
Pipe is in this way, also not the thicker the thickness of solid electrolyte film layer 20 the better.Preferably, the thickness of solid electrolyte film layer 20
For 20nm~300nm.If solid electrolyte film layer 20 is blocked up, material property difference between solid electrolyte and metal, two
Person's binding force is deteriorated, and solid electrolyte film layer 20 is easy to fall off from metal foil 10, and then cannot play and prevent metal foil 10
The effect of dusting.It is further preferred that the solid electrolyte film layer 20 with a thickness of 80nm~120nm.Specific preferred
In embodiment, solid electrolyte film layer 20 with a thickness of 100nm.
DLC film layer 30
20 pairs of water oxygen of solid electrolyte film layer are sensitive, if directly forming solid electrolyte film layer on 10 surface of metal foil
20, then under conditions of there are water oxygen, solid electrolyte film layer 20 will receive destruction, and cannot play prevents 10 dusting of metal foil
Effect.Based on this, need that DLC film is arranged away from the surface of the metal foil 10 in solid electrolyte film layer 20
Layer 30 can protect solid electrolyte film layer 20 by DLC film layer 30, completely cut off water oxygen, prevent it from penetrating into solid-state
Electrolyte thin film layer 20, it is ensured that solid electrolyte film layer 20 gives full play to its function.Meanwhile diamond-like has high rigidity
Advantage can protect solid electrolyte film layer 20 under conditions of ultra-thin, and assign combination electrode excellent toughness and intensity,
Further, since said effect may be implemented in DLC film layer 30 under conditions of relatively thin, avoid blocked up diamond-like thin
Influence of the film layer 30 (is less than point) to battery conductive effect itself.
In the utility model embodiment, the thickness of solid electrolyte film layer 20 is arranged, being capable of effective protection solid-state electricity
Solution matter film layer 20 permeates from water oxygen and does not influence battery conductive effect.Preferably, the thickness of DLC film layer 30
Degree is 10nm~50nm.It if the thickness of DLC film layer 30 is excessively thin, cannot effectively completely cut off water oxygen, and then cannot ensure solid
State electrolyte thin film layer 20 gives full play to its function；If the thickness of DLC film layer 30 is blocked up, lithium ion can be reduced negative
The mobility of pole, or even cause lithium ion mobility difficult, influence the electric property of battery.In addition, DLC film layer 30
Thickness is blocked up, and after 50nm, DLC film layer 30 is obvious in the binding force decline of solid electrolyte film layer 20, is easy
It falls off from solid electrolyte film layer 20.It is further preferred that DLC film layer 30 with a thickness of 15nm~20nm.Having
In body preferred embodiment, DLC film layer 30 with a thickness of 15nm.
On the basis of the above embodiments, as preferred embodiment, in composite negative plate, including it is used as negative pole currect collecting simultaneously
The lithium phosphorus oxynitride layer on one surface of aluminium foil is arranged in the aluminium foil of body and negative electrode active material, and in the lithium phosphorus oxygen
The DLC film layer that nitrogen film layer is arranged away from the surface of the aluminium foil.At this point, obtained composite negative plate has most preferably
Chemical property.Wherein, the lithium phosphorus oxynitride layer, which has, preferably leads lithium performance, can be used as battery material；And institute
It is strong to state stability of the lithium phosphorus oxynitride layer in cell reaction system, the aluminium foil can be subjected to sealing as protective layer,
So that even if aluminum honeycomb will not crush rupture and be detached from, to improve battery when aluminum-copper-lithium alloysization reaction occurs for aluminum honeycomb
High rate performance and cycle performance.But lithium phosphorus oxynitride layer is sensitive to water oxygen.Based on this, carried on the back in lithium phosphorus oxynitride layer
DLC film layer 30 is arranged in surface from aluminium foil, can completely cut off water oxygen by DLC film layer 30 and penetrate into lithium phosphorus oxygen
The influence of nitrogen film layer, it is ensured that lithium phosphorus oxynitride layer gives full play to its function；Meanwhile DLC film layer 30 has height hard
The advantages of spending, so that the protection to lithium phosphorus oxynitride layer may be implemented, and then assign compound aluminum honeycomb under conditions of relatively thin
Piece is preferably wilful, and avoids the influence to ionic conductivity.
Preferably, the lithium phosphorus oxynitride layer with a thickness of 50nm~150nm, the thickness of the DLC film layer
For 10nm~40nm, the aluminium foil with a thickness of 30 μm~90 μm.
It is furthermore preferred that the lithium phosphorus oxynitride layer with a thickness of 80nm~120nm, the thickness of the DLC film layer
Degree be 15nm~20nm, the metal foil with a thickness of 40 μm~60 μm.
It is further preferred that solid electrolyte film layer film layer with a thickness of 100nm, the thickness of DLC film layer 30
Degree be 15nm~20nm, aluminium foil with a thickness of 50 microns.At this point, each thickness degree is suitable, protective barrier layer by layer can not only be formed
(solid electrolyte film layer lithium phosphorus oxynitride layer protects aluminium foil, and DLC film layer 30 protects solid electrolyte film layer
Lithium phosphorus oxynitride layer), and tool is well bonded between each layer.In addition, the clad aluminum that thickness meets above-mentioned requirements is negative
Pole piece has more preferably lithium ion turn-on effect.
Clad aluminum negative electrode tab provided by the embodiment of the utility model is used as negative current collector and negative electrode active material at the same time
10 surface of metal foil set gradually solid electrolyte film layer 20 and DLC film layer 30.Wherein, the solid state electrolysis
Matter layer 20, which has, preferably leads lithium performance, can be improved composite metal negative pole/electrolyte interface ion diffusion rates, improves battery
High rate performance；And the solid-state electrolyte layer 20 can be effectively isolated contact of the composition metal surface with electrolyte, reduce secondary
Reaction process improves battery coulombic efficiency；And the solid-state electrolyte layer 20 can also provide effectively composite metal negative pole
Mechanical protection effect improves composite metal negative pole in electrochemical reaction process because of pulverizing problem caused by volume change, thus
Effectively improve cycle performance of battery.
Clad aluminum negative electrode tab provided by the embodiment of the utility model, can be prepared by following methods.
On the other hand the utility model embodiment provides a kind of preparation method of clad aluminum negative electrode tab, comprising the following steps:
S01., metal foil is provided, the metal foil is successively pre-processed, aura cleaning and ion etching are cleaned；
S02. solid electrolyte target solid electrolyte target deposits solid electrolyte film layer on the surface of the metal foil；
S03. in the surface depositing diamond-like film layer of the solid electrolyte film layer.
Specifically, the metal foil and its thickness selection are as mentioned before in above-mentioned steps S01.Such as the metal foil
With a thickness of 20 microns~150 microns, it is preferred that the metal foil with a thickness of 40 microns~60 microns, more preferably 50 microns.
The metal foil of offer is successively pre-processed, aura cleaning and ion etching cleaning, pass through pretreatment removal gold
Belong to the organic matter on foil surface, especially grease stain；It is removed at substrate surface out-of-flatness such as by aura cleaning and ion etching cleaning
Remaining moisture, gas etc. in scratch, thus to improve the adhesion effect of coating.By gradually cleaning, reach optimal cleaning
Effect has best binding force in the metal foil of coating after cleaning.
In some embodiments, pretreated method is carried out to the metal foil are as follows: successively use distilled water, acetone, nothing
Water-ethanol is cleaned by ultrasonic the metal foil, the organic matter of the metal foil surface especially grease stain is sufficiently removed, so
Dry drying afterwards.
In a particular embodiment, the metal foil is put into distilled water 5~30min of ultrasonic cleaning, then by the metal
Foil is put into 5~30min of ultrasonic cleaning in acetone soln, the metal foil is put into ethanol solution is again cleaned by ultrasonic later
5~30min；After cleaning, substrate surface is dried up with drying nitrogen, finally sample is put into 80 in air dry oven again~
150 DEG C of drying.
After the metal foil is pre-processed, the cleaning of further progress aura.In some embodiments, using pure argon
Aura cleaning is carried out to the metal foil.
Before carrying out aura cleaning, device parameter is adjusted, specifically, the metal foil after drying is fixed on magnetic control
On pivoted frame in sputtering coating equipment；Door for vacuum chamber is closed, opens water cooling unit for ion source, multiple arc target, molecular pump, vacuum chamber
Water route connect, open air compressor machine and composite film coating machine general supply, be then turned on mechanical pump and it is other take out valve and molecular pump, make point
Son pump enters climb mode；After molecular pump reaches full speed, other pumping valve is closed, roughing valve is opened, vacuum chamber is slightly taken out；
After vacuum chamber internal pressure reaches 10Pa or less by force, it is again turned on other pumping valve；After pressure in vacuum tank reaches 3Pa or less, close thick
Valve is taken out, opens high threshold to vacuum chamber pumping high vacuum.When pressure in vacuum tank is extracted into 5.0 × 10-3After Pa, heating power supply is opened to true
Empty room carries out heated baking, and heating temperature is 100~500 DEG C, and turret system is opened in heating process, and sample is made to carry out public affairs certainly
It passes；When vacuum degree reaches 3.0 × 10-3When Pa, start to carry out aura cleaning.
In a particular embodiment, the method for the aura cleaning are as follows: open argon bottle main valve, pressure reducing valve, ion source valve, arc
Valve and target valve and mass flowmenter are passed through argon gas into vacuum chamber, control 300~500sccm of argon flow, and operating pressure is
1.0~1.7Pa, metal foil bias -500V~-800V carry out aura cleaning, 10~30min of scavenging period to metal foil.Upper
Aura cleaning is carried out under the conditions of stating, and hiding can be stayed in moisture, gas in the especially scratch of metal foil out-of-flatness surface
It quickly removes, film adhesion is inadequate when preventing from depositing solid electrolyte film layer subsequently through magnetron sputtering, improves film layer and exists
Binding force in the metal foil.
In order to further ensure moisture, the gas in the especially scratch of metal foil out-of-flatness surface are sufficiently removed,
After aura cleaning, ion etching cleaning is carried out to the metal foil, by relatively soft mode, by metal foil injustice
Moisture, gas in the especially scratch of whole surface completely remove.
In certain embodiments, the method for the ion etching cleaning are as follows: after etch cleaner, open ion source
Icon bombardment cleaning is carried out to sample, wherein ion source voltage is 50~90V, 70~500sccm of argon flow, operating pressure
0.5~1.7Pa, substrate bias are 100~800V.Under the above conditions, the water that can not will have removal in aura cleaning process
Divide and gas completely removes.Preferably, the scavenging period of the icon bombardment cleaning is 10~30min.
The utility model embodiment is by successively pre-processing the metal foil, aura cleans and ion etching is clear
It washes, can step by step, different dynamics remove the various attachments of the metal foil surface, improve coating in the metal foil surface
Adhesive force；Meanwhile surface cleaning is carried out to the metal foil in the method, also there is good timeliness.
In above-mentioned steps S02, solid electrolyte film layer is deposited on the surface of the metal foil, the solid electrolyte is thin
The selection of film layer is as described above, the solid electrolyte film layer can be prepared using vapour deposition process.Wherein, the gas phase is heavy
Area method include magnetron sputtering method, vacuum vapour deposition, arc plasma coating method, ion plating method, molecular beam epitaxy, in gas
Evaporation, sputtering source method, flows vacuum deposition method, metallic vapour synthetic method on pasta at chemical gas-phase reaction method.
As a preferred embodiment, the metal foil is aluminium foil, and the solid electrolyte film layer is lithium phosphorus oxynitride layer,
And in the method for the surface of metal foil deposition solid electrolyte film layer are as follows: once purged metal foil is placed in settling chamber
In, it is passed through nitrogen, adjusting pressure in vacuum tank is 0.2~1.3Pa, opens solid electrolyte target, and control the solid electrolyte
The target power output of target is 30~70W, under conditions of substrate bias is 100~300V, deposits solid-state on the surface of the metal foil
Electrolyte thin film layer.
The preparation method of composite negative plate provided by the embodiment of the utility model, using magnetron sputtering mode, in aluminium foil gold
Belong to foil surface and prepare lithium phosphorus oxynitride layer, and then prepares DLC film layer in lithium phosphorus oxynitride layer.This method passes through
Lithium phosphorus oxynitride layer is prepared, deposition of the lithium phosphorus oxynitride layer on aluminium foil not only may be implemented, and it is thin to assign LiPON
For film layer in the good binding force of aluminium foil surface, film layer is not easily to fall off, but also can accurately control thicknesses of layers, meets battery pole
The requirement of piece.Finally obtained clad aluminum negative electrode tab, caused by can preventing aluminum honeycomb piece i.e. metal foil from rupturing because of crushing
It falls off, and then guarantees the cycle performance of battery.
In the utility model embodiment, once purged aluminium foil is placed in the settling chamber of magnetic-controlled sputtering coating equipment.Institute
It is as shown in Figure 2 to state magnetic-controlled sputtering coating equipment.Nitrogen is passed through in settling chamber, adjusting pressure in vacuum tank is 0.2~1.3Pa, is opened
Lithium phosphate target, and the target power output for controlling the lithium phosphate target is 30~70W, under conditions of substrate bias is 100~300V, is sunk
Product LiPON layer.
In the step of preparing LiPON layer, substrate bias influences binding force of the LiPON layer on aluminium foil, this is practical
New embodiment deposits LiPON layer, obtained LiPON layer is in aluminium foil under conditions of substrate bias is 100~300V
On good bonding strength.
In the step of preparing LiPON layer, the target current and nitrogen flow of the lithium phosphate target have codetermined lithium phosphorus
The quality of oxygen nitrogen layer.If any one in the target current, nitrogen flow changes, lithium, phosphorus, oxygen, nitrogen may be all influenced
Proportion.Preferably, in the step of surface of the aluminium foil deposits LiPON layer, the flow of the nitrogen is 50~
400sccm.The method of LiPON layer provided by the embodiment of the utility model, the target power output and nitrogen partial pressure are in above range
It is interior, the proportion of lithium, phosphorus, oxygen, nitrogen is preferably controlled, faster deposition rate (as shown in Figure 3) and higher ionic conductance are obtained
Rate (is illustrated in fig. 4 shown below).In addition, in the step of preparing LiPON layer, the pressure of vacuum chamber is to obtaining the matter of LiPON layer
Amount has certain influence.The utility model embodiment adjusts pressure in vacuum tank for 0.2~1.3Pa, in obtained LiPON layer
Grain size is suitable, and LiPON layer enhances in the binding force of the aluminium foil surface.And if pressure in vacuum tank is excessively high, deposition velocity
Too fast, obtained LiPON material lattice is chaotic, arrangement is irregular, will affect LiPON layer to the protecting effect of aluminium foil,
In addition, can also reduce LiPON layer in the binding force of the aluminium foil.When pressure in vacuum tank is relatively low, ionic conductivity will affect.
Preferably, in the step of surface of the aluminium foil deposits LiPON layer, be passed through nitrogen, adjust pressure in vacuum tank be 0.6~
0.8Pa.As specific embodiment, it is passed through nitrogen, adjusting pressure in vacuum tank is 0.7Pa.
In some embodiments, the aluminium foil surface deposit LiPON layer the step of in, the lithium phosphate target with
The distance between described aluminium foil is 5 centimetres~15 centimetres.By adjusting lithium phosphate target and the aluminium foil in suitable distance range
It is interior, the proportion of adjustable lithium, phosphorus, oxygen, nitrogen.When the distance between the lithium phosphate target and the aluminium foil are 5 centimetres~15 lis
Meter Shi, obtained LiPON layer ionic conductivity with higher (as shown in Figure 5).Preferably, the lithium phosphate target and institute
Stating the distance between aluminium foil is 7.5cm.
In the utility model embodiment, in the step of surface of the aluminium foil deposits LiPON layer, sedimentation time is
100-140min is preferably but not limited to 120min, thus to obtain the LiPON layer of suitable thickness.Specifically, the lithium phosphorus oxygen
Nitrogen layer with a thickness of 50nm~150nm.Preferably, the LiPON layer with a thickness of 80~120nm, more preferably 100nm.
In above-mentioned steps S03, the surface depositing diamond-like film layer of the solid electrolyte film layer the step of in,
Using acetylene as working gas, and adjusting the indoor pressure of vacuum is 0.5~1.0Pa, and ion source voltage is 50~100V,
Substrate bias is 50~200V, in the transition layer surface depositing diamond-like film layer of the etching sample.
In the step of preparing DLC film layer, the pressure in vacuum tank, ion source voltage and substrate bias are common to determine
The quality of DLC film layer is determined.If any one in the pressure in vacuum tank, ion source voltage and substrate bias becomes
Small, then deposition rate is excessively slow, and sedimentation time is too long；And if any one in pressure in vacuum tank, ion source voltage and substrate bias
Item is excessively high, and deposition velocity is too fast, and the crystal grain arrangement of formation is irregular, so that DLC film layer can be reduced in the transition zone
Binding force.And interrelated between the pressure in vacuum tank, ion source voltage and substrate bias, the variation of arbitrary parameter, all
It may cause deposition effect to change.The Parameter Conditions of transition zone provided by the embodiment of the utility model can to obtain
DLC film layer binding force enhancing, and formed coating dense uniform.
After coating deposits, ion source current and grid bias power supply are closed, it is gentle to be then shut off gas mass flow meter
Bottle main valve and pressure reducing valve；Cooling process is set, after temperature drops to 100 DEG C or less, closes high threshold, vent valve is opened, to vacuum
When indoor pressure is consistent with ambient pressure, door for vacuum chamber is opened, then takes out sample.
In the utility model embodiment, in the step of the surface depositing diamond-like film layer of the solid electrolyte film layer
In rapid, sedimentation time is 100~150s, 2min is preferably but not limited to, thus to obtain the DLC film layer of suitable thickness.Tool
Body, the DLC film layer with a thickness of 10nm~40nm.Preferably, the DLC film layer with a thickness of
15nm~20nm.
The utility model embodiment additionally provides a kind of secondary cell, including anode, cathode, and setting is in the anode and institute
State the diaphragm and electrolyte between cathode, wherein the cathode is clad aluminum negative electrode tab described in the utility model or institute
Stating cathode is the clad aluminum negative electrode tab that method described in the utility model is prepared.
Secondary cell provided by the utility model, cathode are above-mentioned composite negative plate, since the cathode has preferably
Stability, it is thus possible to improve the cycle performance of secondary cell.
Preferably, the anode includes positive electrode active materials, and the positive electrode active materials are selected from expanded graphite, electrically conductive graphite
At least one of with Kynoar.
Preferably, the electrolyte is selected from LiPF6Methyl ethyl carbonate ester solution.Specific preferred, the electrolyte is selected from
LiPF6Concentration is the methyl ethyl carbonate ester solution of 4mol/L
Preferably, the diaphragm is glass fibre.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of clad aluminum negative electrode tab, comprising the following steps:
S11., aluminium foil is provided, the aluminium foil is successively pre-processed, aura cleaning and ion etching are cleaned；It is specific:
The aluminium foil is put into distilled water and is cleaned by ultrasonic, then the aluminium foil is put into acetone soln and is cleaned by ultrasonic, it
The aluminium foil is put into ethanol solution again afterwards and is cleaned by ultrasonic；After cleaning, substrate surface is dried up with drying nitrogen,
Sample is finally put into 80~150 DEG C of drying in air dry oven again.Before carrying out aura cleaning, device parameter, tool are adjusted
Body, the aluminium foil after drying is fixed on the pivoted frame in magnetic-controlled sputtering coating equipment；Door for vacuum chamber is closed, water cooling is opened
Machine connects the water route of ion source, multiple arc target, molecular pump, vacuum chamber, opens air compressor machine and composite film coating machine general supply, then
Mechanical pump and other pumping valve and molecular pump are opened, molecular pump is made to enter climb mode；After molecular pump reaches full speed, close other
Valve is taken out, roughing valve is opened, vacuum chamber is slightly taken out；After vacuum chamber internal pressure reaches 10Pa or less by force, it is again turned on other pumping valve；
After pressure in vacuum tank reaches 3Pa or less, roughing valve is closed, opens high threshold to vacuum chamber pumping high vacuum.When pressure in vacuum tank is taken out
To 5.0 × 10-3After Pa, opens heating power supply and heated baking is carried out to vacuum chamber, heating temperature is 100~500 DEG C, heated
Turret system is opened in journey, and sample is made to carry out public autobiography；When vacuum degree reaches 3.0 × 10-3When Pa, start to carry out aura cleaning.
Argon bottle main valve, pressure reducing valve, ion source valve, arc valve and target valve and mass flowmenter are opened, is led into vacuum chamber
Enter argon gas, control 300~500sccm of argon flow, operating pressure is 1.0~1.7Pa, substrate bias -500V~-800V, right
Substrate carries out aura cleaning.
After etch cleaner, open ion source to sample carry out icon bombardment cleaning, wherein ion source voltage be 50~
90V, 70~500sccm of argon flow, 0.5~1.7Pa of operating pressure, substrate bias are 100~800V.
S12. once purged aluminium foil is placed in settling chamber, is passed through nitrogen, flow 200sccm adjusts vacuum chamber pressure
It is by force 0.2Pa, the target power output opened lithium phosphate target, and control the lithium phosphate target is 50W, in the item that substrate bias is -100V
Under part, deposition 120min prepares LiPON layer.
S13. using acetylene as working gas (main valve of acetylene gas bottle is opened, pressure reducing valve and mass flowmenter are then opened
Acetylene is passed through into vacuum chamber), and adjusting the indoor pressure of vacuum is 0.5Pa, ion source voltage 50V, substrate bias
For 50V, diamond-like rock layers are prepared in the transition layer surface deposition 2min of the etching sample.
S14. after coating deposition, ion source current and grid bias power supply is closed, gas mass flow meter is then shut off
With gas cylinder main valve and pressure reducing valve；Cooling process is set, after temperature drops to 100 DEG C or less, closes high threshold, opens vent valve, to
When vacuum intraventricular pressure is consistent with ambient pressure by force, door for vacuum chamber is opened, then takes out sample.Surface preparation two-layer compound is applied
The aluminium foil of layer is cut, and clad aluminum negative electrode tab is obtained.
Embodiment 2
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: lithium phosphine oxygen nitrogen layer power 50W,
Nitrogen partial pressure 0.5Pa, bias -150V, time 120min.
Embodiment 3
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: lithium phosphine oxygen nitrogen power 50W, nitrogen
Gas divides 0.5Pa, bias -200V, time 120min.
Embodiment 4
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: lithium phosphine oxygen nitrogen power 50W, nitrogen
Gas divides 0.5Pa, bias -250V, time 120min.
Embodiment 5
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: lithium phosphine oxygen nitrogen power 50W, nitrogen
Gas divides 0.5Pa, bias -100V, time 60min.
Embodiment 6
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: lithium phosphine oxygen nitrogen power 50W, nitrogen
Gas divides 0.5Pa, bias -100V, time 90min.
Embodiment 7
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: diamond-like sedimentation time
1min。
Embodiment 8
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: diamond-like sedimentation time
1.5min。
Embodiment 9
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: diamond-like sedimentation time
2.5min。
Embodiment 10
A kind of preparation method of clad aluminum negative electrode tab, difference from example 1 is that: diamond-like sedimentation time
3min。
Comparative example 1
A kind of aluminum honeycomb piece, the aluminum honeycomb piece are aluminium foil identical with embodiment.
The clad aluminum negative electrode tab that embodiment 1-10, comparative example 1 are provided uses expansion stone as battery cathode, anode
Ink, electrolyte use LiPF6Concentration is the methyl ethyl carbonate ester solution of 4mol/L, is assembled into battery.Test the electrochemistry of battery
Energy parameter, test index and test method are as follows:
(1) test index: cycle performance, test method: the circulating ring number of capacity retention ratio 80% under 2C multiplying power；
(2) test index: high rate performance, test method: capacity is kept after respectively recycling 10 circles under 1C~5C~1C multiplying power
Rate；
Test result is as follows shown in table 1, wherein the cell voltage and curve of double curvature figure of embodiment 1 are as shown in fig. 6, battery
Multiplying power vehicle performance curve is as shown in fig. 7, cycle performance of battery is as shown in Figure 8.
Table 1
| Test battery | Circulating ring number | High rate performance |
| Embodiment 1 | 430 | 98% |
| Embodiment 2 | 421 | 96% |
| Embodiment 3 | 425 | 97% |
| Embodiment 4 | 419 | 95% |
| Embodiment 5 | 308 | 90% |
| Embodiment 6 | 353 | 93% |
| Embodiment 7 | 200 | 71% |
| Embodiment 8 | 235 | 79% |
| Embodiment 9 | 304 | 82% |
| Embodiment 10 | 284 | 79% |
| Comparative example 1 | 200 | 50% |
The above is only the preferred embodiment of the utility model only, is not intended to limit the utility model, all at this
Made any modifications, equivalent replacements, and improvements etc., should be included in the utility model within the spirit and principle of utility model
Protection scope within.
Claims (10)
1. a kind of composite negative plate, which is characterized in that the composite negative plate includes while living as negative current collector and cathode
The metal foil of property material, is arranged in the solid electrolyte film layer on one surface of metal foil, and in the solid electrolyte
The DLC film layer that film layer is arranged away from the surface of the metal foil.
2. composite negative plate as described in claim 1, which is characterized in that the composite negative plate is by the metal foil, described
Solid electrolyte film layer and DLC film layer composition, and the metal foil is substrate, the solid electrolyte is thin
Film layer is middle layer, the DLC film layer is outermost layer.
3. composite negative plate as claimed in claim 1 or 2, which is characterized in that the metal foil be selected from aluminium foil, copper foil, iron foil,
One or more of tinfoil paper, silver foil, goldleaf, platinum foil, zinc foil, lead foil, nickel foil；And/or
The solid electrolyte film layer choosing from lithium phosphine oxygen nitrogen layer, polypropylene nitrile layer, polyvinylidene fluoride layer, polyoxyethylene layer,
One or more of silicone layer, sulfide electrolyte layer.
4. composite negative plate as claimed in claim 3, which is characterized in that the metal foil with a thickness of 20~150 μm.
5. composite negative plate as claimed in claim 4, which is characterized in that the metal foil with a thickness of 40~60 μm.
6. composite negative plate as claimed in claim 3, which is characterized in that the solid electrolyte film layer with a thickness of 20~
300nm。
7. composite negative plate as claimed in claim 6, which is characterized in that the solid electrolyte film layer with a thickness of 80~
120nm。
8. composite negative plate as claimed in claim 1 or 2, which is characterized in that the layer of the DLC film is with a thickness of 10
~50nm.
9. composite negative plate as claimed in claim 8, which is characterized in that the layer of the DLC film with a thickness of 15~
20nm。
10. a kind of secondary cell, which is characterized in that including anode, cathode, be arranged between the anode and the cathode every
Film, wherein the cathode is the described in any item composite negative plates of claim 1 to 9.
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| CN201822080185.8U CN209200066U (en) | 2018-12-11 | 2018-12-11 | Composite negative plate, secondary cell |
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|---|---|---|---|
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ID=67428717
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110896141A (en) * | 2019-09-30 | 2020-03-20 | 深圳先进技术研究院 | Element-doped diamond-like carbon film modified battery cathode and preparation method and application thereof |
| WO2020119528A1 (en) * | 2018-12-11 | 2020-06-18 | 深圳先进技术研究院 | Composite negative plate, preparation method therefor and application thereof |
-
2018
- 2018-12-11 CN CN201822080185.8U patent/CN209200066U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020119528A1 (en) * | 2018-12-11 | 2020-06-18 | 深圳先进技术研究院 | Composite negative plate, preparation method therefor and application thereof |
| CN111312994A (en) * | 2018-12-11 | 2020-06-19 | 深圳先进技术研究院 | Composite negative plate and preparation method and application thereof |
| CN110896141A (en) * | 2019-09-30 | 2020-03-20 | 深圳先进技术研究院 | Element-doped diamond-like carbon film modified battery cathode and preparation method and application thereof |
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Assignee: REAL POWER INDUSTRIAL Ltd. Assignor: SHENZHEN INSTITUTES OF ADVANCED TECHNOLOGY Contract record no.: X2022980016102 Denomination of utility model: Composite negative plate, secondary battery Granted publication date: 20190802 License type: Exclusive License Record date: 20220922 |