CN101393979A - Silicon cathode, lithium ion secondary battery comprising the same and manufacturing method therefor - Google Patents
Silicon cathode, lithium ion secondary battery comprising the same and manufacturing method therefor Download PDFInfo
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- CN101393979A CN101393979A CNA2007101406474A CN200710140647A CN101393979A CN 101393979 A CN101393979 A CN 101393979A CN A2007101406474 A CNA2007101406474 A CN A2007101406474A CN 200710140647 A CN200710140647 A CN 200710140647A CN 101393979 A CN101393979 A CN 101393979A
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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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- Y02E60/10—Energy storage using batteries
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Abstract
A silicon negative electrode of a lithium ion secondary battery comprises a conductive matrix and a material layer loaded on the surface of the conductive matrix, wherein the material layer comprises at least a lithium alloy layer and at least a silicon layer; the lithium alloy layer is attached to the conductive matrix; and the lithium alloy layer and the silicon layer are arranged at intervals. In the process of the first charging and discharging for a battery, the silicon negative electrode has the advantages that the irreversible capacity is lower, and the first charging and discharging efficiency is high; the battery prepared by the silicon negative electrode has the better circulation performance; and meanwhile, the battery has the higher volume ratio capacity.
Description
Technical field
The present invention relates to a kind of battery cathode and use the battery of this negative pole and their preparation method, specifically, the present invention relates to a kind of silicium cathode of lithium rechargeable battery and use the lithium rechargeable battery of this silicium cathode and their preparation method.
Background technology
Because it is the fast development and the extensive use of portable electric appts and electric automobile, very urgent for the demand of the lithium ion battery of high-energy-density, long circulation life.The lithium ion battery that commercialization is at present used mainly adopts graphite as negative material, still, because the theoretical specific capacity of graphite only is 372 MAH/grams, therefore, has limited the further raising of lithium ion battery specific energy.Silicon attracts tremendous attention because of having high theoretical lithium storage content (4200 MAH/gram) and low embedding lithium current potential.
Silica-base material with very big change in volume, causes the structural breakdown of electrode material easily and peels off electrode material being lost electrically contact, thereby cause the cycle performance of electrode sharply to descend in the process of removal lithium embedded.
There is research that Si-Mg, Si-Cu, Si-Sn, Si-Fe, SiAlSn or SiAlMn alloy are loaded on the conducting base to attempt to improve the cycle performance of battery, though this method can be improved the cycle performance of battery to a certain extent, cushioned the volumetric expansion of silicon, but the theoretical capacity of battery is lower, simultaneously, the alloy material of cathode ubiquity big problem of irreversible capacity first.
CN1870325A discloses a kind of negative material with lithium rechargeable battery of three-layer cell structure, it is to be coated with active material layer on matrix, wherein, this active material layer employing coating method (as magnetron sputtering method) covers the Si/M/Si material preparation and becomes electrode on the iron foil matrix of Copper Foil, nickel foil, copper facing or nickel plating, described active material layer has the three-layer cell structure of one or more Si/M/Si, described M can for not with metal element Ti, Cr, Mn, Fe, Co, Ni, Cu or the W of lithium reaction; Also can for metallic element Ca, Al, Mg, Ag, Zn, Ge, Sn, Pb, Bi, Sb or the In of lithium reaction.This method can be improved the cycle performance of battery to a certain extent, but, the battery that adopts this silicium cathode preparation is in the first charge-discharge process, the height of irreversible capacity first of silicium cathode material, be that first charge-discharge efficiency is low, the volume and capacity ratio of the lithium rechargeable battery that the silicium cathode that is prepared by this method prepares is less.
Summary of the invention
The objective of the invention is to overcome and adopt the battery that has the silicium cathode preparation now in the first charge-discharge process, the irreversible capacity of silicium cathode material is big, first charge-discharge efficiency is low, the less shortcoming of volume of battery specific capacity for preparing by this silicium cathode, provide a kind of in battery first charge-discharge process, have less irreversible capacity, be the silicium cathode of higher first charge-discharge efficiency and the lithium secondary battery for preparing by this silicium cathode with higher volumes specific capacity and good circulation performance.
The present inventor finds, in the silicium cathode that the CN1870325A disclosed method obtains, though the metal M layer can cushion the lattice dilatation of silicon, but the existence of metal M layer can hinder lithium ion with silicon layer that the conducting base Copper Foil contacts in embedding and deviate from, make the irreversible capacity of this silicium cathode material increase, the silicon layer that contacts with the conducting base Copper Foil simultaneously is not fully utilized, and can cause the negative pole volume and capacity ratio little yet.So-called irreversible capacity is meant in the charge and discharge process first of battery, owing to can not taking off embedding from negative pole, the lithium ion that embeds negative pole make the charge and discharge efficient of electrode less than 100%, promptly Fang Dian electrochemistry capacitance is lower than charging capacity, the part of loss is called irreversible capacity loss, irreversible capacity is high more, and the first charge-discharge efficiency of battery is low more.
The invention provides a kind of silicium cathode of lithium rechargeable battery, described silicium cathode comprises conducting base and is carried on the material layer on this conducting base surface, wherein, described material layer comprises at least one lithium alloy layer and at least one silicon layer, described lithium alloy layer is attached on the conducting base, and described lithium alloy layer and silicon layer are spaced.
The present invention also provides a kind of preparation method of lithium rechargeable battery silicium cathode, described silicium cathode comprises conducting base and is carried on the material layer on this conducting base surface, wherein, described material layer comprises at least one lithium alloy layer and at least one silicon layer, this method comprises and earlier the lithium alloy layer being loaded on the conducting base, then compartment of terrain load upper silicon layer and lithium alloy layer successively.
The present invention also provides a kind of lithium rechargeable battery, this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, silicium cathode and barrier film, wherein, described silicium cathode is a silicium cathode provided by the invention.
The present invention also provides a kind of preparation method of lithium rechargeable battery, this method comprises positive pole and the silicium cathode for preparing this battery, and positive pole, silicium cathode and barrier film are prepared into a pole piece, the pole piece and the electrolyte that obtain are sealed in the battery case, wherein, described silicium cathode makes for adopting method provided by the invention.
In the silicium cathode provided by the invention, be carried on conducting base material at opposite sides layer and comprise at least one lithium alloy layer and at least one silicon layer, described lithium alloy layer is attached on the conducting base, and described lithium alloy layer and silicon layer are spaced.The battery that adopts silicium cathode preparation of the present invention is in the first charge-discharge process, the irreversible capacity first of silicium cathode is lower, be that first charge-discharge efficiency is higher, after making battery along with charge and discharge cycles several times, active material obtains activation gradually, it is more tight that metal in the lithium alloy layer also can combine with the silicon in the silicon layer, this structure can effectively solve because silicium cathode volumetric expansion, pole piece that the lattice dilatation of silicon causes fall problems such as material, avoid the inefficacy of electrode, thereby fully guaranteed the stability of cycle performance of battery.Because the volumetric expansion of silicon pole piece of the present invention is less, so battery also has higher volume and capacity ratio simultaneously.
Embodiment
According to the present invention, the silicium cathode of described lithium rechargeable battery comprises conducting base and is carried on the material layer on this conducting base surface, wherein, described material layer comprises at least one lithium alloy layer and at least one silicon layer, described lithium alloy layer is attached on the conducting base, and described lithium alloy layer and silicon layer are spaced.
Described lithium alloy contains lithium and reaches the element that forms alloy with lithium, and described element with lithium formation alloy is selected from one or more among Ca, Mg, Al, In, Ge, Sn, Pb, Ag, Zn, Cu, Ti, Co, Fe and the Si; More preferably under the situation, can be selected among Si, Zn and the Al one or more in the described lithium alloy layer with the element that lithium forms alloy.
Amount with described lithium alloy is a benchmark, and the content of lithium is 20-80 weight %, is preferably 20-50 weight; The content that forms the element of alloy with lithium is 20-80 weight %, is preferably 50-80 weight %.
The gross thickness of described conducting base surface material layer is the 2-100 micron, is preferably the 2-30 micron; The thickness of every layer of lithium alloy layer is the 1-50 micron, is preferably the 1-20 micron; The thickness of every layer of silicon layer is the 1-50 micron, is preferably the 1-20 micron.
Described negative pole conducting base can be for negative pole conducting base conventional in the lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as the negative pole conducting base in specific embodiments of the present invention.
The preparation method of silicium cathode of the present invention comprises and earlier the lithium alloy layer being loaded on the conducting base, load upper silicon layer then, or compartment of terrain load upper silicon layer and lithium alloy layer successively.
According to the present invention, the method of described load lithium alloy layer and silicon layer is the method for magnetic controlled sputtering ion plating, the method of described magnetic controlled sputtering ion plating lithium alloy layer comprises, under the condition of magnetron sputtering lithium alloy, on the lithium alloy magnetic control target, apply power supply, make the lithium alloy sputter and be deposited on conducting base or silicon layer on; The method of magnetic controlled sputtering ion plating silicon layer comprises, under the condition of magnetron sputtering silicon, applies power supply on magnetic control target, makes the target material silicon sputter of magnetic control target and is deposited on the lithium alloy layer.
Described magnetic controlled sputtering ion plating method can be existing conventional magnetic controlled sputtering ion plating method.For example, described magnetic controlled sputtering ion plating method is included under the sputtering condition, makes the target material sputter of magnetic control target and is deposited on the conducting base applying power supply on the magnetic control target.
Described sputtering condition can be the existing various sputtering conditions that are used for magnetic controlled sputtering ion plating, and it is the 1-50 micron that the condition of magnetron sputtering lithium alloy makes the thickness of every layer of lithium alloy layer, is preferably the 1-20 micron; It is the 1-50 micron that the condition of magnetron sputtering silicon makes the thickness of every layer of silicon layer, is preferably the 1-20 micron, more preferably the 1-10 micron; It is the 2-100 micron that the number of times that spatters control sputter lithium alloy and magnetron sputtering silicon makes the gross thickness of material layer, is preferably the 2-30 micron.
The condition of described magnetron sputtering lithium alloy comprises that pressure (absolute pressure) is the 0.1-1.0 handkerchief, is preferably the 0.5-1.0 handkerchief, and sputtering time is 0.1-20 hour, is preferably 0.1-5 hour; The condition of magnetron sputtering silicon comprises that pressure (absolute pressure) is the 0.1-1.0 handkerchief, is preferably the 0.5-1.0 handkerchief, and sputtering time is 0.1-20 hour, is preferably 0.1-5 hour.
Described power supply can be preferably AC power for AC power or DC power supply, and supply voltage is the 200-600 volt, is preferably the 300-350 volt; Electric current is the 5-30 peace, is preferably the 10-20 peace.
Magnetic controlled sputtering ion plating method of the present invention can be used existing various magnetic controlled sputtering ion plating equipment, and magnetic controlled sputtering ion plating equipment can be commercially available.The structure of described magnetic control target has been conventionally known to one of skill in the art, and for example, magnetic control target can comprise target stand and target, and target is installed on the target stand.Described target stand is a magnet, and described magnet can be existing various magnets, for example, can be in ferromagnet, the neodymium iron boron magnetic body one or more.
According to the present invention, described target material is lithium alloy and silicon, described lithium alloy contains lithium and reaches the element that forms alloy with lithium, and described element with lithium formation alloy is selected from one or more among Ca, Mg, Al, In, Ge, Sn, Pb, Ag, Zn, Co, Fe, Cu, Ti and the Si; One or more among Si, Zn and the Al more preferably.Amount with described lithium alloy is a benchmark, and the content of lithium is 20-80 weight %, is preferably 20-50 weight %, and the content that forms the element of alloy with lithium is 20-80 weight %, is preferably 50-80 weight %.
Described sputtering under the inert gas atmosphere carried out.Described inert gas for example can be helium and/or argon gas for not participating in the gas of sputter reaction; The consumption of described inert gas has been conventionally known to one of skill in the art, for example, as long as the pressure the when consumption of inert gas makes sputter reaches the 0.1-1.5 handkerchief.Can vacuumize earlier, make the absolute pressure in the magnetic controlled sputtering ion plating equipment reach 2 * 10
-3Handkerchief to 6 * 10
-3In the scope of handkerchief, and then charge into inert gas, make the absolute pressure in the magnetic controlled sputtering ion plating equipment reach the 0.1-1.5 handkerchief.
According to the present invention, according to the different needs of different batteries, can on conducting base, form a plurality of lithium alloy layers and a plurality of silicon layer, make described lithium alloy layer and silicon layer stacked arrangement at interval.Under the preferable case, have excellent cycle performance in order to guarantee battery, can make battery have thin as far as possible thickness and higher volume and capacity ratio again, the material layer on described silicium cathode conducting base surface comprises a lithium alloy layer and a silicon layer.
The present invention also provides a kind of lithium rechargeable battery, and this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, silicium cathode and barrier film, described silicium cathode silicium cathode provided by the invention.
Because improvements of the present invention only relate to the silicium cathode of lithium rechargeable battery, therefore in lithium rechargeable battery provided by the invention, positive pole, barrier film and non-aqueous electrolytic solution to battery have no particular limits, and can use all types of positive poles, membrane layer and the non-aqueous electrolytic solution that can use in lithium rechargeable battery.Those of ordinary skill in the art can be according to the instruction of prior art, can select and prepare positive pole, membrane layer and the non-aqueous electrolytic solution of lithium rechargeable battery of the present invention easily, and make lithium rechargeable battery of the present invention by described positive pole, silicium cathode of the present invention, membrane layer and non-aqueous electrolytic solution.
For example, described positive pole can apply and/or be filled on the described collector body by with positive active material, conductive agent and adhesive and solvent, and drying is rolled or do not rolled, and obtains described positive pole; Also can be directly with the positive pole of metal lithium sheet as battery.
Described positive active material is not particularly limited, and can be the positive active material of the embedded removal lithium embedded of this area routine, a kind of or its mixture: the Li in the preferred following material
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur), LimMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0).
Described conductive agent is not particularly limited, and can be the anodal conductive agent of this area routine, at least a such as in acetylene black, conductive carbon black and the electrically conductive graphite.Weight with positive active material is benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
The kind of described anodal adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR).In general, according to the difference of used anodal adhesive kind, be benchmark with the weight of positive active material, the content of anodal adhesive is 0.5-8 weight %, is preferably 1-5 weight %.
Positive electrode collector can be positive electrode collector conventional in the lithium ion battery, uses aluminium foil as positive electrode collector in specific embodiments of the present invention.
Described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described collector body to get final product.In general the weight with positive active material is benchmark, and the content 30-80 weight % of described solvent is preferably 35-60 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9g/Ah, the concentration of electrolyte be generally 0.5-2.9 rub/liter.
Described barrier film is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described pole piece and nonaqueous electrolytic solution are contained in the battery case together.Described barrier film can be selected from various barrier films used in the lithium ion battery, as polyolefin micro porous polyolefin membrane.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
The preparation method of lithium rechargeable battery provided by the invention comprises positive pole, silicium cathode and barrier film is prepared into a pole piece, and pole piece and the electrolyte that obtains is sealed in the battery case, and described silicium cathode is for to be made by method of the present invention.
To do further specific descriptions to the present invention by specific embodiment below, but can not be interpreted as it is qualification protection range of the present invention.
Embodiment 1
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
(1) preparation of silicium cathode
Adopt magnetic controlled sputtering ion plating equipment (multi sphere-magnetron sputtering ion plating machine, Beijing Beiyi Innovation Vacuum Technology Co., Ltd. makes, model is JP-700), with thickness is that 0.01 millimeter conducting base Copper Foil is placed on the work rest in the vacuum chamber of magnetic controlled sputtering ion plating equipment, start vacuum pump and vacuumize, vacuum degree reaches 5 * 10 in vacuum chamber
-3During handkerchief, charge into argon gas, making the absolute pressure in the vacuum chamber is 0.7 handkerchief, and the temperature in the vacuum chamber is transferred to 150 ℃.With two Si targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil is placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 1.5 hours, at thickness is that to form thickness respectively be that 8 microns LiSi layer (prepares the Copper Foil that the multi-disc load has the LiSi alloy-layer according to this method for the both sides of 0.01 millimeter conducting base Copper Foil, getting wherein a slice scrapes alloy-layer and carries out ICP (inductance coupled plasma emission spectrum) test, the content that records Li is about 40 weight %, and the content of Si is about 60 weight %).Close power supply on the Li target (voltage is 400 volts, and electric current is 15 peaces) then, and continued plated film 40 minutes, on described LiSi layer, obtain thickness respectively and be 4 microns Si film.At last, be of a size of 34 millimeters * 50 millimeters * 0.024 millimeter silicium cathode, wherein contain promising 0.1 gram negative electrode active material silicon approximately through cutting to make.
(2) assembling of battery
Silicium cathode, Celgard barrier film and 10 purity that 11 steps (1) are made are of a size of 34 millimeters * 50 millimeters * 1.0 millimeters the folded successively pole piece of making a stacked battery of metal lithium sheet greater than 99.9 weight %, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, this electrolyte is injected aluminum plastic film with the amount of 3.2g/Ah, stacked flexible packing lithium ion battery Al is made in sealing.
Embodiment 2
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares lithium rechargeable battery, and different is in the preparation process of silicium cathode, with two Al targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil to be placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 30 minutes, at thickness is that to form thickness respectively be 8 microns LiAl (content that records Li according to the method for embodiment 1 is about 40 weight %, and the content of Al is about 60 weight %) layer for the both sides of 0.01 millimeter conducting base Copper Foil.Close the power supply on Li target, the Al target then, and with two parallel respectively being placed in the magnetic control sputtering device of Si target, the conducting base Copper Foil is placed in the middle of two targets, (voltage is 400 volts to start the power supply that is applied on the silicon target, electric current is 15 peaces), and continued plated film 40 minutes, on described LiAl layer, obtain thickness respectively and be 4 microns Si film.And prepare flexible-packed battery A2.
Embodiment 3
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares lithium rechargeable battery, and different is in the preparation process of silicium cathode, with two Si targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil to be placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 1.5 hours, at thickness is that to form thickness respectively be 15 microns LiSi layer (content that records Li according to the method for embodiment 1 is about 15 weight %, and the content of Si is about 85 weight %) for the both sides of 0.01 millimeter conducting base Copper Foil.Close the power supply on the Li target then, and continued plated film 1.2 hours, on described LiSi layer, obtain thickness respectively and be 8 microns Si film.And prepare flexible-packed battery A3.
Embodiment 4
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares lithium rechargeable battery, and different is in the preparation process of silicium cathode, with two Cu targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil to be placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 1 hour, at thickness is that to form thickness respectively be 15 microns LiCu layer (content that records Li according to the method for embodiment 1 is about 20 weight %, and the content of Cu is about 80 weight %) for the both sides of 0.01 millimeter conducting base Copper Foil.Close the power supply on Li target and the Cu target then, and with two parallel respectively being placed in the magnetic control sputtering device of Si target, the conducting base Copper Foil is placed in the middle of two targets, (voltage is 400 volts to start the power supply that is applied on the silicon target, electric current is 15 peaces), and continued plated film 1.5 hours, on described LiCu layer, obtain thickness respectively and be 12 microns Si film.And prepare flexible-packed battery A4.
Embodiment 5
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares lithium rechargeable battery, and different is in the preparation process of silicium cathode, with two Zn targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil to be placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 20 minutes, at thickness is that to form thickness respectively be 6 microns LiZn layer (content that records Li according to the method for embodiment 1 is about 40 weight %, and the content of Zn is about 60 weight %) for the both sides of 0.01 millimeter conducting base Copper Foil.Close the power supply on Li target, the Zn target then, and, the conducting base Copper Foil is placed in the middle of two targets with two parallel respectively being placed in the magnetic control sputtering device of Si target, start the power supply that is applied on the silicon target, and continued plated film 50 minutes, on described LiZn layer, obtain thickness respectively and be 5 microns Si film.And prepare flexible-packed battery A5.
Embodiment 6
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares lithium rechargeable battery, and different is in the preparation process of silicium cathode, with two Fe targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil to be placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 30 minutes, at thickness is that to form thickness respectively be 8 microns LiFe layer (content that records Li according to the method for embodiment 1 is about 30 weight %, and the content of Fe is about 70 weight %) for the both sides of 0.01 millimeter conducting base Copper Foil.Close the power supply on Li, the Fe target then, and, the conducting base Copper Foil is placed in the middle of two targets with two parallel respectively being placed in the magnetic control sputtering device of Si target, start the power supply that is applied on the silicon target, and continued plated film 40 minutes, on described LiFe layer, obtain thickness respectively and be 4 microns Si film.And prepare flexible-packed battery A6.
Embodiment 7
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares lithium rechargeable battery, and different is in the preparation process of silicium cathode, with two Ti targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil to be placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 1.2 hours, at thickness is that to form thickness respectively be 8 microns LiTi layer (content that records Li according to the method for embodiment 1 is about 40 weight %, and the content of Ti is about 60 weight %) for the both sides of 0.01 millimeter conducting base Copper Foil.Close the power supply on Li target, the Ti target then, and, the conducting base Copper Foil is placed in the middle of two targets with two parallel respectively being placed in the magnetic control sputtering device of Si target, start the power supply that is applied on the silicon target, and continued plated film 40 minutes, on described LiTi layer, obtain thickness respectively and be 4 microns Si film.And prepare flexible-packed battery A7.
Embodiment 8
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares lithium rechargeable battery, and different is, in the preparation process of silicium cathode, with two Si targets, two Al targets and two parallel respectively being placed in the magnetic control sputtering device of Li target, the conducting base Copper Foil is placed in the middle of two targets.
(voltage is 400 volts to start the power supply that is applied on the magnetic control target simultaneously, electric current is 15 peaces), under said temperature and pressure condition, sputter 1.5 hours, at thickness is that to form thickness respectively be that (content that records Li according to the method for embodiment 1 is about 20 weight % for 12 microns LiSiAl layer for the both sides of 0.01 millimeter conducting base Copper Foil, the content of Si is about 30 weight %, and the content of Al is 50 weight %).Close the power supply on Li target, the Al target then, and continued plated film 20 minutes, on described LiSiAl layer, obtain thickness respectively and be 2 microns Si film.And prepare flexible-packed battery A8.
Embodiment 9
Present embodiment illustrates the preparation of lithium rechargeable battery provided by the invention
Method according to embodiment 1 prepares battery, different is, in the preparation process of silicium cathode, load one deck LiSi alloy again on the Si film, it is 4 microns that the condition of sputter makes the thickness of the LiSi layer that obtains (content that records Li according to the method for embodiment 1 is about 40 weight %, and the content of Si is about 60 weight %).And be prepared into flexible-packed battery A9 according to the method for embodiment 1.
Comparative Examples 1
The preparation of this Comparative Examples explanation reference lithium rechargeable battery
Method according to embodiment 1 prepares the reference lithium rechargeable battery, and different is in the preparation of silicium cathode, with two parallel being placed in the magnetic control sputtering device of Si target, the conducting base Copper Foil to be placed in the middle of two targets.Start the power supply (regulation voltage to 400 volt, electric current are 15 peaces) be applied on the magnetic control target simultaneously, under said temperature and pressure condition, sputter 2 hours is that to form thickness respectively be 12 microns Si film for the both sides of 0.01 millimeter conducting base Copper Foil at thickness.Then this Si negative pole and metal Li sheet are formed half-cell, note is reference cell B1.
Comparative Examples 2
The preparation of this Comparative Examples explanation reference lithium rechargeable battery
Method according to the disclosed embodiment 1 of CN1870325A prepares the silicium cathode with Si/Fe/Si three-decker, and the thickness of Si layer is 4 microns in this silicium cathode, and the gross thickness of two-layer Si layer is 8 microns; The Fe layer thickness is 4 microns.And prepare reference flexible-packed battery B2 according to the method for embodiment 1.
Comparative Examples 3
The preparation of this Comparative Examples explanation reference lithium rechargeable battery
Method according to Comparative Examples 2 prepares the silicium cathode with three-decker, and different is that the Fe layer replaces with the SiSn alloy of 4 micron thickness.And prepare the reference flexible-packed battery according to the method for embodiment 1 and will prepare reference cell B4.
Embodiment 10-18
This embodiment illustrates the performance test of lithium rechargeable battery provided by the invention
1, cycle performance of battery test:
Under 25 ℃, the battery A1-A9 that embodiment 1-9 is prepared (is higher than anodal current potential with metal lithium sheet as the negative pole current potential of the lithium rechargeable battery of positive pole, therefore need discharge earlier to recharge) with the current discharge of design capacity 0.05C 4 hours, it is 4.2 volts with the current discharge of design capacity 0.1C 6 hours to voltage again, and then, it is 10 milliamperes extremely by electric current with 4.2 volts of discharges of constant voltage; Constant current charge to cell voltage with 1C is 3.0 volts again.Discharge with actual capacity 1C again, and charge with actual capacity 1C, the discharge capacity first and the initial charge capacity of record battery, repeat to discharge and recharge 100 times, discharge capacity after the record battery circulation 100 times, and first charge-discharge efficiency, capability retention and the volume of battery specific capacity of counting cell according to the following equation:
First charge-discharge efficiency=initial charge capacity (taking off lithium) (MAH)/first discharge capacity (embedding lithium) (MAH)
Capability retention (%)=(discharge capacity of the circulation of discharge capacity/first of the 100th circulation) * 100%.
Volume and capacity ratio (MAH/centimetre
3)=be battery first discharge capacity (MAH)/negative plate volume (centimetre
3).
The result is as shown in table 1.
2, cell thickness test:
Measure respectively the battery A1-A9 for preparing by embodiment 1-9 after carrying out charge and discharge cycle first thickness and the thickness of the 100th circulation back battery, described thickness comprises chucking thickness and lax thickness, described chucking thickness is for adopting the cell thickness that measures behind the vernier caliper chucking, and described lax thickness is the thickness of the battery that adopts calliper and measure.
The result is as shown in table 1.
Comparative Examples 4-6
The performance test of this Comparative Examples explanation reference lithium rechargeable battery
Method according to embodiment 10-18 is carried out performance test to lithium rechargeable battery, and different is the reference lithium rechargeable battery B1-B3 that the battery of test prepares for the method that adopts Comparative Examples 1-3.
Table 1
Result from last table 1 as can be seen, the first charge-discharge efficiency of the silicium cathode battery of the battery A1-A9 that is prepared by embodiment 1-9 is all more than 85%, the irreversible capacity that is silicium cathode is less, after circulation 100 times, the capacity sustainment rate of battery all can remain on more than 86%, all obviously is better than reference cell; And the volume of battery specific capacity also significantly is better than reference cell in first charge-discharge circulation back.
Claims (12)
1, a kind of silicium cathode of lithium rechargeable battery, described silicium cathode comprises conducting base and is carried on the material layer on this conducting base surface, it is characterized in that, described material layer comprises at least one lithium alloy layer and at least one silicon layer, described lithium alloy layer is attached on the conducting base, and described lithium alloy layer and silicon layer are spaced.
2, silicium cathode according to claim 1, wherein, described lithium alloy contains lithium and reaches the element that forms alloy with lithium, and described element with lithium formation alloy is selected from one or more among Ca, Mg, Al, In, Ge, Sn, Pb, Ag, Zn, Cu, Ti, Co, Fe and the Si.
3, silicium cathode according to claim 2, wherein, described element with lithium formation alloy is selected from one or more among Si, Zn and the Al.
4, silicium cathode according to claim 2 wherein, is a benchmark with the amount of described lithium alloy, and the content of lithium is 20-80 weight %, and the content that forms the element of alloy with lithium is 20-80 weight %.
5, silicium cathode according to claim 1, wherein, the gross thickness of conducting base surface material layer is the 2-100 micron; The thickness of every layer of lithium alloy layer is the 1-50 micron, and the thickness of every layer of silicon layer is the 1-50 micron.
6, the preparation method of the described silicium cathode of claim 1, described silicium cathode comprises conducting base and is carried on the material layer on this conducting base surface, it is characterized in that, described material layer comprises at least one lithium alloy layer and at least one silicon layer, this method comprises that elder generation loads on the lithium alloy layer on the conducting base, load upper silicon layer then, or compartment of terrain load upper silicon layer and lithium alloy layer successively.
7, method according to claim 6, wherein, the method of load lithium alloy layer and silicon layer is the method for magnetic controlled sputtering ion plating, the method of described magnetic controlled sputtering ion plating lithium alloy layer comprises, under the condition of magnetron sputtering lithium alloy, on the lithium alloy magnetic control target, apply power supply, make the lithium alloy sputter and be deposited on conducting base or silicon layer on; The method of described magnetic controlled sputtering ion plating silicon layer comprises, under the condition of magnetron sputtering silicon, applies power supply on magnetic control target, makes the target material silicon sputter of magnetic control target and is deposited on the lithium alloy layer.
8, method according to claim 7, wherein, it is the 1-50 micron that the condition of magnetron sputtering lithium alloy makes the thickness of every layer of lithium alloy layer, it is the 1-50 micron that the condition of magnetron sputtering silicon makes the thickness of every layer of silicon layer, and it is the 2-100 micron that the number of times that spatters control sputter lithium alloy and magnetron sputtering silicon makes the gross thickness of material layer.
9, method according to claim 8, wherein, the condition of magnetron sputtering lithium alloy comprises that pressure is the 0.1-1.0 handkerchief, sputtering time is 0.1-20 hour; The condition of magnetron sputtering silicon comprises that pressure is the 0.1-1.0 handkerchief, and sputtering time is 0.1-20 hour.
10, according to claim 6 or 7 described methods, wherein, described lithium alloy contains lithium and reaches the element that forms alloy with lithium, and described element with lithium formation alloy is selected from one or more among Ca, Mg, Al, In, Ge, Sn, Pb, Ag, Zn, Cu, Ti, Co, Fe and the Si; Amount with described lithium alloy is a benchmark, and the content of lithium is 20-80 weight %, and the content that forms the element of alloy with lithium is 20-80 weight %.
11, a kind of lithium rechargeable battery, this battery comprises pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, silicium cathode and barrier film, it is characterized in that described silicium cathode is any described silicium cathode among the claim 1-5.
12, the preparation method of the described lithium rechargeable battery of claim 11, this method comprises positive pole, silicium cathode and barrier film is prepared into a pole piece, the pole piece and the electrolyte that obtain are sealed in the battery case, it is characterized in that any described method makes described silicium cathode among the claim 6-9 in order to adopt.
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| CN104810511A (en) * | 2015-04-10 | 2015-07-29 | 苏州靖羽新材料有限公司 | Anode material of electrical equipment and electrical equipment |
| CN108063222A (en) * | 2017-08-31 | 2018-05-22 | 广东猛狮新能源科技股份有限公司 | A kind of lithium ion battery negative material, its preparation method and lithium ion battery |
| CN109244355A (en) * | 2017-07-11 | 2019-01-18 | 天津中能锂业有限公司 | Preparation mends the method for the cathode of lithium, mends the cathode and lithium ion secondary battery of lithium |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3520921B2 (en) * | 2001-03-27 | 2004-04-19 | 日本電気株式会社 | Negative electrode for secondary battery and secondary battery using the same |
| CN1870325A (en) * | 2006-05-26 | 2006-11-29 | 南开大学 | Lithium ion secondary battery negative plate material with three-layer cell structure and preparation method |
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2007
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810511A (en) * | 2015-04-10 | 2015-07-29 | 苏州靖羽新材料有限公司 | Anode material of electrical equipment and electrical equipment |
| CN109244355A (en) * | 2017-07-11 | 2019-01-18 | 天津中能锂业有限公司 | Preparation mends the method for the cathode of lithium, mends the cathode and lithium ion secondary battery of lithium |
| CN109244355B (en) * | 2017-07-11 | 2021-08-24 | 天津中能锂业有限公司 | Method for producing lithium-supplemented negative electrode, and lithium ion secondary battery |
| CN108063222A (en) * | 2017-08-31 | 2018-05-22 | 广东猛狮新能源科技股份有限公司 | A kind of lithium ion battery negative material, its preparation method and lithium ion battery |
| CN108063222B (en) * | 2017-08-31 | 2024-04-02 | 广东猛狮新能源科技股份有限公司 | Lithium ion battery negative electrode material, preparation method thereof and lithium ion battery |
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