CN100517854C - Lithium secondary battery and method of manufacturing the same - Google Patents
Lithium secondary battery and method of manufacturing the same Download PDFInfo
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- CN100517854C CN100517854C CNB2005101200909A CN200510120090A CN100517854C CN 100517854 C CN100517854 C CN 100517854C CN B2005101200909 A CNB2005101200909 A CN B2005101200909A CN 200510120090 A CN200510120090 A CN 200510120090A CN 100517854 C CN100517854 C CN 100517854C
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Abstract
The invention provides a lithium secondary battery having a high discharge capacity and an excellent cycle characteristic. This lithium secondary battery includes a negative electrode having a negative electrode active material 2 and a negative electrode current collector, a positive electrode having a positive electrode active material 1 and a positive electrode current collector 3, and a nonaqueous electrolyte. The lithium secondary battery is characterized in that, as the negative electrode active material 2, a material that is increased in volume by alloying with lithium during charge is used; the negative electrode is composed by arranging the negative electrode active material 2 so as to contact with the surface of the negative electrode current collector; and the negative electrode active material 2 contains, in a discharge ended state, 8% or more of lithium with respect to the total capacity of the negative electrode active material 2 as measured when it does not contain lithium.
Description
Technical field
The present invention relates to lithium secondary battery and manufacture method thereof, specifically, relate to as negative electrode active material and used lithium secondary battery and manufacture method thereof with the material of lithium alloyage.
Background technology
Though at negative electrode active material as lithium secondary battery, used under the situation of carbon class material, the expansion of the negative electrode active material during charging is little, but using under the such situation with material lithium alloyage of silicon, the volumetric expansion of the active material during charging just becomes about about 4 times, reaches very large volume.Thus, when the material with alloying uses as negative electrode active material, will be owing to making active material expand shrink because of discharging and recharging, because of consequent stress makes active material break away from, current collection variation, thereby the problem that has cycle characteristics to worsen.
In patent documentation 1, discovery is by making film like with silicon isoreactivity material, the prismatical structure that the crack that formation is formed by the thickness direction along film is separated just can be alleviated by the expansion of active material and shrink the stress that causes, and can improve cycle characteristics significantly.
In addition, in patent documentation 2, record following situation, that is, use and to utilize the electrochemical negative electrode active material that contains lithium ion in the silicon that is reflected at, suppress to improve cycle characteristics by overcharging and the generation of the irreversible material that overdischarge causes.
In addition, in patent documentation 3, record following method, that is, in the lithium secondary battery that carbon class material is used as negative electrode active material,, on negative pole, attach the lithium metal and make battery for the cell degradation that suppresses to cause by overdischarge.
But, in the lithium secondary battery of the negative pole that the silicon thin film of having been announced in having used by patent documentation 1 etc. constitutes with prismatical structure, not in negative electrode active material in advance the situation of elements doped lithium study, its effect is not identified yet.
[patent documentation 1] international literary composition volume that discloses No. 0129913
[patent documentation 2] spy opens flat 7-29602 communique
[patent documentation 3] spy opens flat 5-144472 communique
Summary of the invention
The objective of the invention is to, when using charging as negative electrode active material because of with the lithium secondary battery of the material of lithium alloyage volume increase in, the lithium secondary battery and the manufacture method thereof of discharge capacity height and cell excellent in cycle characteristics are provided.
The invention provides possess negative pole with negative electrode active material and negative electrode collector, the lithium secondary battery of positive pole, nonaqueous electrolyte, it is characterized in that, as negative electrode active material, use because of when the charging and the material of lithium alloyage volume increase, by negative electrode active material is constituted negative pole according to the mode setting that directly is contacted with on the negative electrode collector, under the discharge done state, contain the lithium more than 8% of the total capacity under the state that does not contain lithium of negative electrode active material at negative electrode active material.
According to the present invention, by under the discharge done state of each charge and discharge cycles, contain the lithium more than 8% of the total weight of the negative electrode active material under the state that does not contain lithium at negative electrode active material, just can improve cycle characteristics.Since when discharge lithium from negative electrode active material, emit, though the therefore volume contraction of negative electrode active material, the part of emitting reaction of the easiest generation lithium is near the strongest collector body of electric field when discharging.When lithium was emitted, the volume contraction of active material produced fine be full of cracks on the surface of active material.When producing more this kind be full of cracks near collector body, near the intensity of the active material the collector body will reduce, just peel off at this part active material with collector body, and the current collection variation, cycle characteristics reduces.In the present invention, because under the discharge done state, therefore make the lithium more than 8% of the total capacity that contains negative electrode active material in the negative electrode active material,, also can suppress the generation of the fine be full of cracks on aforesaid active material surface even under the discharge done state.Thus, just can prevent active material peeling off from the collector body, keep current collection well, can obtain good cycle characteristics.And, among the present invention, in " being contained in the lithium in the negative electrode active material ", also comprise attached to the lithium in the coverlay of the lithium compound on negative electrode active material surface.
Discharge done state of the present invention is the state of cell voltage when having reached in the lithium secondary battery of made by predefined discharge end voltage.Under the situation that transition metal oxides such as the cobalt/cobalt oxide that will contain lithium, the nickel oxide that contains lithium, Mn oxide use as positive active material, in general, the end voltage of will discharging is set at about 2.75V, and the state when having arrived this discharge end voltage is the discharge done state.
In addition, do not contain the total capacity of the negative electrode active material under the state of lithium, can it be charged to current potential reach 0V, try to achieve according to the charging capacity of the 1st circulation of this moment by making negative pole as the three electric pole type batteries that the effect utmost point uses.And, in three electric pole type batteries, with lithium metal as using to electrode and with reference to the utmost point.
The amount of the lithium that negative electrode active material contained is more than 8% of total capacity as mentioned above under the discharge done state, more preferably more than 20%.Though the upper limit of the lithium amount that is contained in the negative electrode active material is not particularly limited, and is in general preferred below 80%.
Negative electrode active material of the present invention be when charging because of with the material of lithium alloyage volume increase, for example can enumerate silicon, tin, aluminium etc.In addition, negative electrode active material of the present invention is provided with according to the mode that directly is contacted with on the negative electrode collector.So, be not that folder is bonded on the negative electrode collector every binding agent etc.For example, can enumerate from gas phase or liquid phase the film stack of negative electrode active material and the mode that forms.As the method for build-up film from gas phase, can enumerate CVD method, sputtering method, vapour deposition method, metallikon etc.As the method for build-up film from liquid phase, can enumerate coating methods such as electrolytic film plating method or electroless plating embrane method.
The electrode that negative pole of the present invention is preferably as follows promptly, is separated into column along the crack that the thickness direction of film forms with this film as the utilization of being announced in the patent documentation 1, and the bottom of this stylolitic part and negative electrode collector connect airtight.By forming this kind electrode structure, around stylolitic part, be formed with the space, the expansion that therefore just can utilize this gap to accept active material is shunk, thereby can prevent the generation of stress.The crack of the thickness direction of this kind active material film preferably utilizes the expansion of the accumulation that is caused by discharging and recharging of active material film and shrinks and forms.Particularly, be easy to produce the crack when having on the collector body surface when concavo-convex.That is, become the film of active material, on the surface of the film of active material, also can form concavo-convex corresponding concavo-convex with as the collector body surface of basalis by have heap-shaped on the concavo-convex collector body on the surface.In the zone that the concavo-convex paddy portion on the paddy portion that this kind film is concavo-convex, collector body surface links, form density regions easily, along this kind density regions, form the crack, by it film is separated into column.
Preferred amorphous of negative electrode active material of the present invention or microcrystalline film.In addition, preferred silicon thin film of this film or silicon alloy film.As silicon alloy, preferably contain the alloy of the above silicon of 50 atom %, for example can enumerate Si-Co alloy, Si-Fe alloy, Si-Zn alloy, Si-Zr alloy etc.
Among the present invention, the lithium more than 8% in the negative electrode active material under the discharge done state preferably brings by pre-elements doped lithium in discharging and recharging the forward direction negative electrode active material.That is, preferably pass through pre-elements doped lithium in negative electrode active material in advance, the lithium in the active material under the discharge done state is made as more than 8%.
The manufacture method of lithium secondary battery of the present invention is to make the method for described lithium secondary battery of the present invention, it is characterized in that, comprising: prepare the negative pole, positive pole, nonaqueous electrolyte before the battery assembling and the operation of battery external packing body that these negative poles, positive pole and nonaqueous electrolyte are taken in; Pre-elements doped lithium in discharging and recharging the forward direction negative electrode active material is so that contain the operation of the lithium more than 8% at negative electrode active material under the discharge done state; Finish the operation of the lithium secondary battery that negative pole, positive pole, nonaqueous electrolyte and battery external packing body by the pre-lithium that mixed constitute.
As the method for pre-elements doped lithium in discharging and recharging the forward direction negative electrode active material, can enumerate the method for utilizing the pre-elements doped lithium of electrochemical method.For example, can enumerate following method, that is, negative pole and lithium metal are immersed in the nonaqueous electrolyte, the pre-doping in negative electrode active material from the lithium of lithium metal.In addition, can also enumerate following method, that is, making with lithium metal be battery to electrode, charges elements doped lithium in advance in the negative electrode active material of negative pole by the negative pole before the battery assembling.
As the operation of pre-doping of the present invention, can preferably use negative pole and lithium metal be impregnated in method in the nonaqueous electrolyte.As concrete method, can enumerate following method, promptly, configuration negative pole and positive pole in battery external packing body, and make under a part of state of contact of lithium metal and negative pole, nonaqueous electrolyte is being imported in the battery external packing body, from lithium metal pre-elements doped lithium to negative electrode active material.Make the preferred negative electrode active material of not facing mutually with the positive active material of positive pole in the zone of negative pole of lithium metal contact or the zone of negative electrode collector.So, be preferably on the negative electrode active material in the negative pole zone that does not press from both sides every barrier film and face mutually with the positive active material of positive pole or the negative electrode collector lithium metal be set.
In the manufacture method of the present invention, the electrode that more preferably will attach lithium metal on negative electrode active material or negative electrode collector in advance uses as negative pole.As mentioned above, the zone that attaches lithium metal does not preferably press from both sides every barrier film and the zone faced mutually with the positive active material of positive pole.When on negative electrode active material, attaching lithium metal, near the negative electrode active material the part that has attached lithium metal, be doped with a large amount of lithiums in advance.So, be made as not the zone of facing mutually with positive pole by the zone that will be like this in advance be doped with a large amount of lithiums, just can reduce the reduction of the capacity that causes because of elements doped lithium in advance.
Because pre-the doping, the lithium metal that is accommodated in the battery external packing body disappears because of lithium is entrained in the negative electrode active material in advance.In addition, the preferred lithium metal that uses the amount that disappears.
Under negative pole and anodal situation about being accommodated under the state that the barrier film coincidence is reeled by folder in the battery external packing body, the interior perimembranous and the outermost perimembranous that are preferably in the negative pole of reeling condition attach lithium metal.Because lithium is local cell reaction from the suction storage of lithium metal to negative electrode active material, therefore when lithium being inhaled in the negative pole integral body that storage reeled, to spend the more time.By earlier lithium metal separately being attached to the interior perimembranous and the outermost perimembranous of negative pole, just can shorten lithium is inhaled the time of storing in the negative pole integral body.In addition, by lithium metal being attached on the more position, just this time can be shortened further.
When under with negative pole and anodal state of reeling, being accommodated in the battery external packing body as mentioned above, the operation that the operation of insertion lithium metal will thicken between negative pole and barrier film.In such cases, metal formings such as Copper Foil are installed, on this metal forming, attach lithium metal, just can easily carry out the attaching operation of lithium metal by peripheral end at negative pole.
The amount of the lithium metal that uses in order to mix in advance among the present invention can be utilized following formula, by the area S (cm that forms the zone of negative electrode active material
2), be equivalent to per unit area the capacity C (mAh/cm of pre-lithium amount of mixing
2) try to achieve.
Lithium metal amount M (g)=(C * 3.6/96500) * 6.94 * S
In described formula, 3.6 for being used for capacity (mAh) is scaled the value of electric weight (C: coulomb), and 96500 is Faraday constant, and 6.94 is the atomic weight of lithium.And 1mAh is with 1.0 * 10
-3Electric weight when A flows through 1 hour electric current, 1C (coulomb) are the electric weight when flowing through 1 second electric current with 1A.So, 1mAh=3.6C (coulomb).
As the method that lithium metal is attached on negative electrode active material or the negative electrode collector, can enumerate the method that lithium metal is pressed against on negative electrode active material layer or the negative electrode collector and attaches.
Among the present invention, the collector body surface preferably has been formed as described above concavo-convex.So, preferably with the collector body surface roughening.More than the preferred 0.1 μ m of the arithmetic average roughness Ra on collector body surface, more preferably 0.1～1 μ m.Arithmetic average roughness Ra is stipulated by JIS (JIS B 0601-1994).Arithmetic average roughness Ra for example can utilize surface roughometer to measure.
As method, can enumerate coating method, vapor growth method, etching method and polishing etc. with the collector body surface roughening.Coating method and vapor growth method are by on the collector body of being made by metal forming, be formed on the surface and have concavo-convex thin layer, and with the method for surface roughening.As coating method, can enumerate electrolytic film plating method and electroless plating embrane method.In addition, as vapor growth method, can enumerate sputtering method, CVD method, vapour deposition method etc.In addition, as etching method, can enumerate the etching or the chemical etching method that utilize physics.In addition, as polishing, can enumerate the grinding that utilizes sand paper or utilize grinding of sandblast etc.
Collector body of the present invention is preferably formed by the conductive metal paper tinsel.As the conductive metal paper tinsel, for example can enumerate metals such as copper, nickel, iron, titanium, cobalt or the metal forming of the alloy made by their combination.The material that especially preferably contains the metallic element that in active material, spreads easily.As this kind material, can enumerate the metal forming that contains copper, particularly Copper Foil or copper alloy foil.As copper alloy foil, preferably use the thermal endurance copper alloy foil.So-called thermal endurance copper alloy is meant, the copper alloy of tensile strength more than 300MPa after 200 ℃ of annealing of 1 hour.As this kind thermal endurance copper alloy, for example can use material cited in the table 1.In order to increase arithmetic average roughness Ra, preferably use on this kind thermal endurance copper alloy foil and utilize electrolysis to be provided with the collector body of copper layer or copper alloy layer.
Table 1
| Title | Form |
| Add tin copper | In copper, add 0.05～0.2% tin, the phosphorus below 0.04% |
| Add silver-bearing copper | In copper, add 0.08～0.25% silver |
| Zirconium copper (using in an embodiment) | In copper, add 0.02～0.2% zirconium |
| Chromium-copper | In copper, add 0.4～1.2% chromium |
| Titanium copper | In copper, add 1.0～4.0% titanium |
| Beryllium copper | In copper, add 0.4～2.2% plating and a spot of cobalt, nickel and iron |
| Add iron copper | In copper, add 0.1～2.6% iron, 0.01～0.3% phosphorus |
| High-strength brass | In the brass of cupric 55.0～60.5%, add the aluminium below 2.0%, the manganese below 3.0%, the iron below 1.5% |
| Add one-ton brass | Copper by 80.0～95.0%, 1.5～3.5% tin and remaining zinc constitute |
| Phosphor bronze | As principal component, contain 3.5～9.0% tin, 0.03～0.35% phosphorus with copper |
| Aluminium bronze | Contain 77.0～92.5% copper, 6.0～12.0% aluminium, 1.5～6.0% iron, the nickel below 7.0%, the manganese below 2.0% |
| Copper-nickel alloy | As principal component, contain 9.0～33.0% nickel, 0.40～2.3% iron, 0.20～2.5% manganese, the following zinc of 1.0 % with copper |
| The steel nickel silicon alloy | In copper, contain 3% nickel, 0.65% silicon, 0.15% manganese |
| The CrZr copper alloy | In copper, contain 0.2% chromium, 0.1% zirconium, 0.2% zinc |
Among the present invention,, can LiPF be shown example though the solute of nonaqueous electrolyte is not specially limited
6, LiBF
4, LiCF
3SO
3, LiN (CF
3SO
2)
2, LiN (C
2F
5SO
2)
2, LiN (CF
3SO
2) (C
4F
9SO
2), LiC (CF
3SO
2)
3, LiC (C
2F
5SO
2)
3, LiAsF
6, LiClO
4, Li
2B
10Cl
10, Li
2B
12Cl
12Deng and their mixture.
Though the solvent of employed nonaqueous electrolyte is not specially limited in the lithium secondary battery of the present invention, use as long as can be used as the solvent of lithium secondary battery.As solvent, preferred cyclic carbonate or linear carbonate.As cyclic carbonate, can enumerate ethylene carbonate, propene carbonate, butylene, vinylene carbonate etc.Wherein, especially preferably use ethylene carbonate.As linear carbonate, can enumerate dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate etc.In addition as solvent, preferably with the solvent more than 2 kinds mixed solvent.The mixed solvent that especially preferably contains cyclic carbonate and linear carbonate.In addition, also can in solvent, also contain vinylene carbonate.Below the preferred 20 weight % of the meltage of vinylene carbonate.By the dissolving vinylene carbonate, just can further improve cycle characteristics.
In addition, also can preferably use described cyclic carbonate and 1,2-dimethoxy-ethane, 1, the mixed solvent of ether solvents such as 2-diethoxyethane.
In addition, among the present invention,, also can be the gelatinous polymer electrolyte that in polymer dielectrics such as poly(ethylene oxide), polyacrylonitrile, has flooded electrolyte as electrolyte, LiI, Li
3Inorganic solid electrolytes such as N.
In addition, among the present invention, in nonaqueous electrolyte, also can be dissolved with carbon dioxide.By dissolved carbon dioxide, just can prevent the situation of repeatedly carrying out porous of negative electrode active material, thereby can further improve cycle characteristics because of discharging and recharging.As the meltage of carbon dioxide, more than the preferred 0.01 weight %, more preferably more than the 0.1 weight %.
As positive active material of the present invention, can LiCoO be shown example
2, LiNiO
2, LiMn
2O
4, LiMnO
2, LiCo
0.5N
0.5O
2, LiNi
0.7Co
0.2Mn
0.1O
2Deng lithium-containing transition metal oxide, MnO
2Deng the metal oxide that does not contain lithium.In addition, in addition, so long as the material that lithium electrochemical ground is inserted, breaks away from can use ad lib.
According to the present invention, can form the lithium secondary battery of discharge capacity height and cell excellent in cycle characteristics.
Description of drawings
Fig. 1 is the figure of section of the electrode group coiling body of expression embodiments of the invention.
Fig. 2 is surface (a) and the surface (c) of the back side (b) and negative pole and the vertical view of the back side (d) of the positive pole of expression embodiments of the invention.
Fig. 3 is expression other the figure of section of electrode group coiling body of embodiment of the present invention.
Fig. 4 is the figure of state of the negative pole of the charged state after the ageing of expression embodiment 13.
Fig. 5 is the figure of state of the negative pole of the charged state after the ageing of expression embodiment 14.
Wherein, 1 ... positive active material, 2 ... negative electrode active material, 3 ... collector body, 4 ... barrier film, 5～10 ... lithium metal, 11 ... positive electrode collector, 11a～11d ... the zone of uncoated positive active material
Embodiment
To illustrate in further detail the present invention based on embodiment below, but the present invention is not subjected to any qualification of following embodiment, in the scope that does not change its purport, can suitably changes enforcement.
(experiment 1)
[making of negative pole]
To roll on the surface of copper alloy foil in thermal endurance, and utilize electrolysis to separate out copper and copper alloy foil (arithmetic average roughness Ra:0.25 μ m, the thickness: 25 μ m) use of surface roughening as collector body.On this collector body, pile up amorphous silicon membrane under the conditions shown in Table 2, made electrode.Here, though the electric energy of using as sputter is supplied with DC pulse, also can under same condition, carry out sputter with direct current or high frequency.And, in the table 2, be standard cubic centimeter per minutes as the sccm of the unit of flow.
Table 2
| The DC pulse frequency | 100kHz |
| The DC pulse width | 1856ns |
| DC pulse power | 2000W |
| Argon flow amount | 60sccm |
| Gas pressure | 2.0～2.5×10 -1Pa |
| The accumulation time | 175 minutes |
| Thickness | 6μm |
The film of gained is cut into the size of 25mm * 25mm with collector body, has made negative pole.
[making of electrolyte A]
In the solvent that propene carbonate (PC), diethyl carbonate (DEC) are mixed with volume ratio at 9: 1, dissolve LiPF
6, make it to reach 1 mol, made electrolyte A.
[making of electrolyte B]
In electrolyte A100 mass parts, add vinylene carbonate (VC), make it to reach 2 weight portions, made electrolyte B.
[mensuration of the total capacity of negative pole]
Measured the total capacity of the negative pole under the state that does not contain lithium.Specifically, made described negative pole used as the effect utmost point and with the lithium metal as to electrode and with reference to three electric pole type batteries of utmost point use, with 1mAh/cm
2Current density charge, until reaching 0V (vs.Li/Li
+) current potential, try to achieve the 1st time the circulation charging capacity, with its total capacity as negative pole.Consequently, the total capacity as negative pole can obtain 5.0mAh/cm
2Value.As electrolyte, used under any one the situation of electrolyte A and electrolyte B all identical.
[anodal making]
As initiation material, use Li
2CO
3And CoCO
3, according to making Li: the atomic ratio of Co reaches 1: 1 mode weighing, mixes with mortar, with its die stamping with diameter 17mm, behind the press molding, in air, burns till under 800 ℃ 24 hours, has obtained LiCoO
2Sintered body.It is pulverized with mortar, average grain diameter is modulated to 20 μ m.
LiCoO with gained
2Powder 90 weight portions, be blended in the N-methyl pyrrolidone solution that comprises as 5 weight % of Kynoar 5 weight portions of binding agent, made the anode mixture slip as Delanium powder 5 weight portions of conductive agent.
This anode mixture slip is coated on the aluminium foil as collector body, rolls after the drying.With the material stamping-out of gained is 20mm * 20mm, has made positive pole.
[mensuration of anodal total capacity]
Use described positive pole, make three electric pole type batteries, tried to achieve anodal total capacity.Specifically, with 1mAh/cm
2Current density discharge and recharge, until reaching 2.75V～4.3V (vs.Li/Li
+) potential range, try to achieve the 1st time the circulation discharge capacity, as the total capacity of positive pole.Total capacity as positive pole has obtained 2.6mAh/cm
2Value.Having used under any one the situation of electrolyte A and electrolyte B all is identical value.
[the pre-doping of anticathode]
Made described negative pole as the effect utmost point, lithium metal as to electrode and with reference to the utmost point, and has been used the three electric pole type batteries of electrolyte A, charged, made charging capacity reach 0.88mAh (0.14mAh/cm respectively to 5 negative poles
2), 2.36mAh (0.38mAh/cm
2), 3.83mAh (0.61mAh/cm
2), 6.25mAh (1.0mAh/cm
2) and 12.5mAh (1.6mAh/cm
2), to each negative pole lithium that mixed in advance.With these electrodes as electrode a1～a5.These electrodes that carried out pre-doping are used by 2 one group ground making as battery A1～A5 and battery B1～B5 respectively.
In addition, with the electrode that mixes in advance as electrode a0.
[making of battery]
(embodiment 1～4 and comparative example 1～2)
Use described electrode a0～a5, described positive pole, described electrolyte A to make lithium secondary battery.Specifically, folder forms the electrode group every the barrier film of being made by porous polyethylene between positive pole and negative pole, and this electrode group is inserted in the battery external packing body of being made by lamination aluminium.Then, described electrolyte A is injected 500 μ l, made battery A0～A5.And the design capacity of these batteries is 10.4mAh.
(embodiment 5～8 and comparative example 3～4)
Except using electrolyte B, with the described battery B0～B5 that made in the same manner.
And the design capacity of these batteries is 10.4mAh.
[evaluation of charge-discharge characteristic]
For described battery A0～A5 and B0～B5, estimated charge.With each battery after charging to 4.2V with the current value of 10.4mA under 25 ℃, be discharged to 2.75V with the current value of 10.4mA, with its discharging and recharging as 1 circulation.The charging capacity and the discharge capacity of the 1st circulation are illustrated in the table 3.In addition,, calculate remaining Li and measure, be illustrated in the table 3 by the charging capacity of the 1st circulation and discharge capacity, with the capacity that three electric pole type batteries have mixed in advance.In addition, utilize following formula to calculate the Li ratio by remaining Li amount.The Li ratio is the remaining ratio of Li with respect to the total capacity of the negative electrode active material under the discharge done state.
Li ratio (%)=(the remaining Li amount after the initial stage discharges and recharges)/(total capacity of negative pole) * 100
In addition, under described charge and discharge cycles condition, carry out discharging and recharging of 50 circulations, try to achieve the discharge capacity and the capacity sustainment rate of the 50th circulation, be illustrated in the table 3.And the capacity sustainment rate is calculated with following formula.
Capacity sustainment rate (%)=(discharge capacity of the 50th circulation)/(discharge capacity of the 1st circulation) * 100
Table 3
In addition, also estimate in the same manner, evaluation result is illustrated in the table 4 with described for battery B0～B5.
Table 4
Remaining Li amount (mAh)=[charging capacity (mAh/cm of the 1st circulation
2Discharge capacity (the mAh/cm of)-the 1st time circulation
2)]+capacity (mAh/cm that mixed in advance
2)
Can be clear that from table 3 and table 4, reach more than 8% by making the Li ratio that the discharge capacity of the 50th circulation and capacity sustainment rate improve, discharge capacity and cycle characteristics improve.In addition, reach more than 20% by making the Li ratio, discharge capacity and cycle characteristics further improve.
Can be clear that from the comparison of table 3 and table 4 by contain vinylene carbonate in nonaqueous electrolyte, discharge capacity and cycle characteristics are further improved.
(experiment 2)
[making of negative pole]
Make except piling up amorphous silicon membrane under the conditions shown in Table 5 the electrode, made negative pole in the same manner with experiment 1.
Table 5
| The DC pulse frequency | 100kHz |
| The DC pulse width | 1856ns |
| DC pulse power | 2000W |
| Argon flow amount | 60sccm |
| Gas pressure | 2.0～2.5×10 -1Pa |
| The accumulation time | 146 minutes |
| Thickness | 5μm |
At the negative pole to gained, utilization is 3.8mAh/cm after having used three electric pole type batteries of lithium to try to achieve total capacity in to electrode and reference extremely
2
The negative pole of gained is cut into the size of 33.5mm * 240mm with collector body, negative pole current collection joint is installed and has been made negative pole.
[anodal making]
Made positive pole in the same manner with experiment 1.
After the positive pole to gained utilizes three electric pole type batteries to try to achieve total capacity, be 2.6mAh/cm
2
With the anodal stamping-out of gained is the size of 31.5mm * 262mm, anodal current collection joint is installed and has been made positive pole.This anodal entire area is expressed as 165cm with the two sides
2, the dispensing area of the active material on the collector body is expressed as 105cm with the two sides
2
[making of battery]
(embodiment 9)
Fig. 2 is the vertical view of described positive pole of expression and negative pole.The anodal surface of Fig. 2 (a) expression, the anodal back side of Fig. 2 (b) expression, the surface of Fig. 2 (c) expression negative pole, the back side of Fig. 2 (d) expression negative pole.
Shown in Fig. 2 (a), positive pole forms by coating positive active material 1 on positive electrode collector 11.Shown in Fig. 2 (a), when reeling positive pole, be positioned on the inboard end and be formed with the regional 11b that positive active material 1 is not set.In addition, on the end of the position outside when reeling, being positioned at, also be formed with the regional 11a that positive active material 1 is not set with bigger area.In addition, similarly, shown in Fig. 2 (b), go up overleaf, when reeling, be positioned on the inboard end and also be formed with the regional 11d that positive active material 1 is not set, on the end that is positioned at the outside, be formed with the regional 11c that positive active material 1 is not set with bigger area.In the outside of positive pole positive terminal 12 is installed.When reeling positive pole, reeled toward the outer side in the back side shown in Fig. 2 (b).
In addition, as Fig. 2 (c) and (d), in negative pole, the surface of negative electrode collector 13 and the back side comprehensively on be formed with negative electrode active material 2.In the outside of negative pole, anode connector 14 is installed.
Use described positive pole and negative pole to make lithium secondary battery.Folder forms the electrode group every the barrier film of being made by porous polyethylene between positive pole and negative pole, after the volume core that this electrode group is used diameter 18mm is reeled, carries out punching press.
Fig. 1 is the profile of the state of the electrode group having represented so to reel.As shown in Figure 1, be formed with positive active material 1 and do not press from both sides the zone of facing mutually every barrier film 4 with negative electrode active material 2.Can in the zone that this is not faced mutually, insert lithium metal 5～10 respectively.Inserted lithium metal to the position of reference numbering 8 in the present embodiment.And lithium metal inserts in argon gas atmosphere.The amount of lithium metal is 30mg.
After as mentioned above coiling body being inserted in the battery external packing body that constitutes by the aluminium layered product, injecting 1g and test 1 same electrolyte B, made battery C1.The design capacity of this battery is 274mAh.In addition, after injecting electrolyte, lithium metal is utilized in the negative electrode active material that electrochemical reaction is entrained in negative pole in advance, and lithium metal disappears.
(comparative example 5)
Except in coiling body, do not insert beyond the lithium metal, with the described battery C2 that made in the same manner.
[evaluation of charge-discharge characteristic]
For described battery C1 and C2, estimated charge.With each battery after charging to 4.2V with the current value of 274mA under 25 ℃, carried out the constant voltage discharge with 4.2V, until the current value that reaches 13.7mA.Thereafter being discharged to cell voltage with 274mA is 2.75V, with its discharging and recharging as 1 circulation.Discharge and recharge under this condition to 40 circulations, each battery has been calculated the capacity sustainment rate that defines by following formula.
Discharge capacity * 100 of the discharge capacity/1st time circulation of capacity sustainment rate (%)=40th time circulation
And the charging capacity of the 1st circulation, discharge capacity, remaining Li amount and Li ratio are calculated in the same manner with experiment 1.The results are shown in the table 6.
Table 6
Can be clear that from the result shown in the table 6, lithium metal is contacted with negative pole, among the battery C1 of the embodiment 9 of the lithium that mixed in advance in the negative electrode active material of negative pole, discharge capacity improves, and the capacity sustainment rate also improves.So, illustrate that discharge capacity and cycle characteristics improve.
As mentioned above, according to the present invention, by under the discharge done state according to the mode of the lithium more than 8% of the total capacity that contains negative electrode active material, be entrained in lithium in the negative electrode active material in advance, just can prevent the situation of repeatedly carrying out deterioration of negative electrode active material, thereby can obtain high discharge capacity and good cycle characteristics because of circulation.
(experiment 3)
(embodiment 10)
Except 2 identical with experiment, makes coiling shown in Figure 1 electrode, Fig. 1 with reference to the position of numbering 6 on beyond the lithium metal of attaching 12mg, made battery in the same manner with embodiment 9.
(embodiment 11)
In embodiment 10, except Fig. 1 with reference to numbering 5 position on attached the lithium metal of 30mg, having attached on the position with reference to numbering 6 beyond the lithium metal of 12mg, similarly made battery.
(embodiment 12)
In embodiment 10, except Fig. 1 with reference to numbering 5 position on attached the lithium metal of 20mg, on position, attached the lithium metal of 12mg with reference to numbering 6, having attached on the position with reference to numbering 9 beyond the lithium metal of 10mg, similarly made battery.
With these batteries 60 ℃ of following ageings after 3 days, measured the weight of lithium metal.The result is as follows.
Embodiment 10:15mg
Embodiment 11:9.5mg
Embodiment 12:7mg
According to above found that, with lithium metal is attached to 1 position on compare, separately be attached to the enhanced dissolution rate that a plurality of locational sides can make lithium metal, thereby can make negative electrode active material inhale the storage lithium quickly.So,, just can shorten the time of ageing operation by lithium metal separately is attached on a plurality of positions.
(experiment 4)
Use discharge capacity to be 2.6mAh/cm
2Positive pole and discharge capacity be 3.0mAh/cm
2Negative pole, attach the 20mg lithium metal as followsly, made battery in the same manner with embodiment 9.
(embodiment 13)
In the present embodiment, only on the position of Fig. 1, attached the lithium metal of 20mg with reference to numbering 6.
(embodiment 14)
In the present embodiment, on the position of Fig. 1, attached the lithium metal of 10mg, on position, attached the lithium metal of 10mg with reference to numbering 6 with reference to numbering 5.
Carried out after the ageing at battery, charged, until reaching 4.35V, charged with constant voltage thereafter, until reaching 14mA with the constant current of 273mA to the negative pole that used described embodiment 13 and 14.
The battery of charged state is disassembled, observed the state of negative pole.
Fig. 4 is the figure of state of the negative pole of expression embodiment 13, and Fig. 4 is the figure of state of the negative pole of expression embodiment 14.
From Fig. 4, can be clear that, install in the negative pole of embodiment 13 of lithium metal at 1 position, observe with negative pole zone that positive pole is faced mutually on separated out the situation of lithium metal.In contrast, in the embodiment 14 that lithium metal is installed separately on a plurality of positions, as shown in Figure 5, do not observe separating out of lithium metal.
(experiment 5)
Fig. 3 represents in the same manner negative pole and anodal folder to be overlapped the electrode group of having reeled every barrier film with experiment 2.Among the embodiment shown in Figure 3, Copper Foil 16 is installed the peripheral end of negative pole 2 ground connection that is electrically connected.By lithium metal 15 is installed on the Copper Foil of so being installed 16, the installation procedure of lithium metal is oversimplified.So the rate of finished products that battery is made also improves.
Claims (24)
1. lithium secondary battery is the lithium secondary battery that possesses negative pole with negative electrode active material and negative electrode collector, positive pole, nonaqueous electrolyte, it is characterized in that,
As described negative electrode active material, only use because of when the charging and the material of lithium alloyage volume increase, by described negative electrode active material is constituted negative pole according to the mode setting that directly is contacted with on the described negative electrode collector, under the discharge done state, in described negative electrode active material, include the lithium more than 8% of the total capacity under the state that does not contain lithium of described negative electrode active material.
2. lithium secondary battery according to claim 1, it is characterized in that, described negative pole is to pile up the film of described negative electrode active material and the electrode that forms at described negative electrode collector from gas phase or liquid phase, this electrode is following electrode, and promptly this film of crack that is formed by the thickness direction along this film bottom and described negative electrode collector of being separated into column and this stylolitic part connects airtight.
3. lithium secondary battery according to claim 1 is characterized in that, described negative electrode active material is amorphous or microcrystalline film.
4. lithium secondary battery according to claim 2 is characterized in that, described negative electrode active material is amorphous or microcrystalline film.
5. lithium secondary battery according to claim 3 is characterized in that, described film is silicon thin film or silicon alloy film.
6. lithium secondary battery according to claim 4 is characterized in that, described film is silicon thin film or silicon alloy film.
7. according to any described lithium secondary battery in the claim 1～6, it is characterized in that described negative electrode active material is a silicon alloy.
8. according to any described lithium secondary battery in the claim 1～6, it is characterized in that, the lithium 8% or more in the described negative electrode active material under the described discharge done state, by before discharging and recharging in described negative electrode active material in advance elements doped lithium bring.
9. lithium secondary battery according to claim 7 is characterized in that, the lithium 8% or more in the described negative electrode active material under the described discharge done state, by before discharging and recharging in described negative electrode active material in advance elements doped lithium bring.
10. the manufacture method of a lithium secondary battery is a method of making any described lithium secondary battery in the claim 1～9, comprising:
The operation of the battery external packing body of preparing the described negative pole before the battery assembling, described positive pole, described nonaqueous electrolyte and they being taken in;
Pre-elements doped lithium in discharging and recharging the described negative electrode active material of forward direction is so that contain the operation of described lithium more than 8% at described negative electrode active material under described discharge done state;
Finish the operation of the lithium secondary battery that constitutes by the negative pole of the pre-described lithium that mixed, described positive pole, described nonaqueous electrolyte and described battery external packing body.
11. the manufacture method of lithium secondary battery according to claim 10 is characterized in that, the operation of described pre-doping comprises the operation that electrochemically lithium is entrained in advance in the described negative electrode active material.
12. the manufacture method of lithium secondary battery according to claim 10, it is characterized in that, described pre-doping operation comprises following operation, promptly, described negative pole of configuration and described positive pole in described battery external packing body, and make under a part of state of contact of lithium metal and described negative pole, described nonaqueous electrolyte is being imported in the described battery external packing body, from described lithium metal pre-elements doped lithium to described negative electrode active material.
13. the manufacture method of lithium secondary battery according to claim 11, it is characterized in that, described pre-doping operation comprises following operation, promptly, described negative pole of configuration and described positive pole in described battery external packing body, and make under a part of state of contact of lithium metal and described negative pole, described nonaqueous electrolyte is being imported in the described battery external packing body, from described lithium metal pre-elements doped lithium to described negative electrode active material.
14. the manufacture method of lithium secondary battery according to claim 12, it is characterized in that, make the zone of the described negative pole of described lithium metal contact be the described negative electrode active material do not faced mutually with the positive active material of described positive pole or the zone of described negative electrode collector.
15. the manufacture method of lithium secondary battery according to claim 13, it is characterized in that, make the zone of the described negative pole of described lithium metal contact be the described negative electrode active material do not faced mutually with the positive active material of described positive pole or the zone of described negative electrode collector.
16. the manufacture method of lithium secondary battery according to claim 12, it is characterized in that, described negative pole and described positive pole are accommodated in the described battery external packing body under the state that barrier film overlap to be reeled at folder, are pasted with described lithium metal in the interior perimembranous and the outermost perimembranous of the negative pole of this reeling condition.
17. the manufacture method of lithium secondary battery according to claim 13, it is characterized in that, described negative pole and described positive pole are accommodated in the described battery external packing body under the state that barrier film overlap to be reeled at folder, are pasted with described lithium metal in the interior perimembranous and the outermost perimembranous of the negative pole of this reeling condition.
18. the manufacture method of lithium secondary battery according to claim 14, it is characterized in that, described negative pole and described positive pole are accommodated in the described battery external packing body under the state that barrier film overlap to be reeled at folder, are pasted with described lithium metal in the interior perimembranous and the outermost perimembranous of the negative pole of this reeling condition.
19. the manufacture method of lithium secondary battery according to claim 15, it is characterized in that, described negative pole and described positive pole are accommodated in the described battery external packing body under the state that barrier film overlap to be reeled at folder, are pasted with described lithium metal in the interior perimembranous and the outermost perimembranous of the negative pole of this reeling condition.
20. the manufacture method according to any described lithium secondary battery in the claim 12～19 is characterized in that described lithium metal is separated to be attached to a plurality of positions.
21. the manufacture method according to claim 16 or 17 described lithium secondary batteries is characterized in that, at the peripheral end of described negative pole metal forming is installed, and attaches described lithium metal on this metal forming.
22. the manufacture method of lithium secondary battery according to claim 20 is characterized in that, at the peripheral end of described negative pole metal forming is installed, and attaches described lithium metal on this metal forming.
23. the manufacture method according to any described lithium secondary battery in the claim 12～19 is characterized in that, the electrode that will attach described lithium metal on described negative electrode active material or described negative electrode collector in advance uses as described negative pole.
24. the manufacture method of lithium secondary battery according to claim 20 is characterized in that, the electrode that will attach described lithium metal on described negative electrode active material or described negative electrode collector in advance uses as described negative pole.
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| JP5425504B2 (en) * | 2009-03-27 | 2014-02-26 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| US8920953B2 (en) | 2010-01-13 | 2014-12-30 | Panasonic Corporation | Lithium ion secondary battery including an elastic member arranged inside an electrode assembly and method for producing the same |
| JP6359836B2 (en) * | 2014-02-07 | 2018-07-18 | 信越化学工業株式会社 | Negative electrode material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery |
| WO2017010129A1 (en) | 2015-07-10 | 2017-01-19 | 太陽誘電株式会社 | Electrochemical device |
| TW201826607A (en) * | 2016-09-08 | 2018-07-16 | 日商麥克賽爾控股股份有限公司 | Lithium ion secondary battery and method for manufacturing same |
| CN206451767U (en) | 2016-12-27 | 2017-08-29 | 宁德新能源科技有限公司 | A kind of takeup type battery core |
| JP6866202B2 (en) * | 2017-03-28 | 2021-04-28 | 太陽誘電株式会社 | Electrochemical device |
| US11670756B2 (en) * | 2017-11-02 | 2023-06-06 | The University Of Tokyo | Negative electrode for secondary battery, secondary battery, and manufacturing methods thereof |
| US11145891B2 (en) * | 2018-04-24 | 2021-10-12 | Panasonic Intellectual Property Management Co., Ltd. | Lithium metal secondary battery and method for producing the same |
| KR20200062427A (en) * | 2018-11-26 | 2020-06-04 | 주식회사 엘지화학 | Method for preparing lithium secondary battery |
| CN111969266A (en) * | 2020-09-01 | 2020-11-20 | 上海空间电源研究所 | Cylindrical lithium ion battery capable of automatically pre-lithiating and preparation method thereof |
| CN118661277A (en) * | 2022-08-08 | 2024-09-17 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery and electricity utilization device |
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