CN102694158A - Silicon-containing lithium cathode, preparation method thereof and lithium sulfur battery with silicon-containing lithium cathode - Google Patents
Silicon-containing lithium cathode, preparation method thereof and lithium sulfur battery with silicon-containing lithium cathode Download PDFInfo
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Abstract
本发明涉及一种含硅锂负极、其制备方法及包含该负极的锂硫电池。该锂负极制备方法包括：步骤1，将含硅负极材料与导电剂、粘结剂混合涂布在集流体上，干燥，制备含硅材料极片；以该含硅材料极片为正极，金属锂片为负极，组装电池，在0.01V~2V之间以10~1000mA/g电流密度进行放电-充电循环，得到电化学预储锂的含硅锂负极片；步骤2，将上述放电至0.01V完成储锂步骤的电池，继续放电，得到电化学过量沉积锂的含硅锂负极片。本发明提供的用于锂硫电池的含硅锂负极，使用高容量的含硅材料负极材料作为载体，通过电化学方法补充锂源，与传统的锂箔负极比较，比表面积更大，降低了枝晶形成的概率，减少金属锂用量，电池循环性能和安全性能都会有所改善。
The invention relates to a silicon-containing lithium negative electrode, a preparation method thereof and a lithium-sulfur battery comprising the negative electrode. The preparation method of the lithium negative electrode includes: step 1, mixing and coating the silicon-containing negative electrode material with a conductive agent and a binder on the current collector, drying, and preparing a silicon-containing material pole piece; using the silicon-containing material pole piece as a positive electrode, metal The lithium sheet is used as the negative electrode, and the battery is assembled, and the discharge-charge cycle is performed at a current density of 10-1000mA/g between 0.01V and 2V to obtain a silicon-containing lithium negative electrode sheet for electrochemically pre-storing lithium; step 2, discharge the above to 0.01 V The battery that has completed the lithium storage step continues to discharge to obtain a silicon-containing lithium negative electrode sheet that electrochemically over-deposits lithium. The silicon-containing lithium negative electrode for lithium-sulfur batteries provided by the present invention uses a high-capacity silicon-containing material negative electrode material as a carrier, and supplements the lithium source by an electrochemical method. Compared with the traditional lithium foil negative electrode, the specific surface area is larger, and the The probability of dendrite formation, reducing the amount of lithium metal, battery cycle performance and safety performance will be improved.
Description
Technical field
The invention belongs to technical field of chemical power, particularly, relate to a kind of preparation method of siliceous cathode of lithium and comprise the lithium-sulfur cell of this negative pole.
Background technology
Lithium-sulfur cell is to receive much attention in recent years and drop into the high-energy density secondary Green Chemistry power supply of more research.Be that anodal lithium-sulfur cell electrochemical reaction is following: S with the elemental sulfur
8+ Li Li
2S
x (1≤
x≤8) Li
2S.According to final reduction reaction product Li
2S calculates, and the theoretical specific capacity of elemental sulfur is 1672mAh/g, and lithium metal has theoretical specific capacity 3860mAh/g, and the theoretical energy density of Li/S redox couple is up to 2600Wh/kg.Lithium-sulfur cell has the characteristics of high-energy-density, in electrokinetic cell of future generation, has the potentiality of extensive use.
Traditional lithium-sulfur cell generally adopts metallic lithium foil as negative pole; But cathode of lithium constantly dissolves, deposits in the charge and discharge cycles process; Be prone to produce dendrite, " dead lithium "; Cause cycle performance of battery to descend, dendrite can diaphragm cause internal short-circuit with anodal the contact when serious, has potential safety hazard on fire or blast takes place.
In the lithium ion battery, siliceous negative material has the high advantage of gram specific capacity.If silicon materials electrochemistry continues the excess deposition lithium on electrode hole, surface after storing up lithium alloyage fully simultaneously, can remedy the capacitance loss that the replacement metal lithium electrode causes, alleviate negative pole weight.Silicon can also play the effect of machinery frame in battery charging process, disperse lithium atom, and the inhibition lithium metal is in negative pole/electrolyte interface enrichment and produce Li dendrite; And suitably excessive lithium helps to protect silicon, makes silicon be in the shallow lithium state that takes off, and reduces change in volume, and it is stable to keep negative pole structure.
But silicium cathode itself does not contain " lithium source ", and the lithium ion that can't provide the lithium-sulfur cell electrochemical reaction to provide can't be formed an electrochemical system with sulphur.Therefore need store up lithium or excess deposition lithium in advance to material.
Summary of the invention
The purpose of this invention is to provide the preparation method of a kind of lithium-sulfur cell with siliceous cathode of lithium; Through using material to be carrier; Both can it be stored up full lithium fully through electrochemical method and use as negative pole, also can after storing up lithium, further remake at its surface electrochemistry excess deposition lithium is that negative pole uses.This negative pole has reduced the consumption of lithium metal in the electrode, has improved the surface area of lithium electrode, improves the cycle performance and the fail safe of lithium-sulfur cell to a certain extent.
For realizing above purpose, the invention provides a kind of preparation method of siliceous cathode of lithium, this method comprises following concrete steps:
Step 2; The siliceous negative plate of preparation excess deposition lithium metal: the above-mentioned 0.01V that is discharged to is accomplished the battery that stores up the lithium step; Continue discharge with 10 ~ 1000mA/g current density; At siliceous cathode of lithium sheet surface electrochemistry excess deposition lithium metal, to the lithium metal capacity of excess deposition be 0 ~ 2 times that material is stablized lithium storage content, obtain the siliceous cathode of lithium sheet of electrochemistry excess deposition lithium.
The preparation method of above-mentioned siliceous cathode of lithium, wherein, said siliceous negative material is selected to have more than in the active silicon/carbon composite of electrochemical lithium storage, silicon/nanocarbon/metal composite material, the silicon-base oxide composite material any one.
The present invention also provides a kind of siliceous cathode of lithium that makes according to above-mentioned method that comprises; Wherein, This siliceous cathode of lithium be with Copper Foil as collector, siliceous negative material is as carrier, behind full lithium ion of carrier inside storage or the full lithium of storage again at carrier surface excess deposition lithium metal.
The present invention also provides a kind of lithium-sulfur cell that comprises the siliceous cathode of lithium that above-mentioned method makes, and wherein, this battery comprises described siliceous cathode of lithium, sulphurous materials positive pole, electrolyte, barrier film, shell.
Above-mentioned lithium-sulfur cell, wherein, more than any one in described sulphurous materials selection elemental sulfur, sulphur/carbon composite, sulfide polymer, the organic polysulfide.
Novel siliceous cathode of lithium proposed by the invention is to use the lithium ion battery material negative pole of high power capacity to carry out electrochemistry as carrier to store up in advance/lithium deposition, and the amount of electrochemical deposition lithium can be controlled according to demand flexibly, and adjustable extent is big.The material electrode is porous state simultaneously, is carrier with it, and is bigger in the specific area of its surface electrochemistry precipitated lithium metal, under identical electric current, can reduce the current density of electrode, reduces the probability that dendrite forms; Substitute conventional metallic lithium foil negative pole with it, reduce the lithium metal consumption, cycle performance of battery and security performance all have bigger improvement.
Description of drawings
Fig. 1 prepares the process sketch map for siliceous cathode of lithium of the present invention, and the first step is a silicon materials storage lithium process, when the storage lithium is accomplished, carries out second step, i.e. the excess deposition lithium metal.
Fig. 2 is the material negative pole storage lithium and the excess deposition lithium metal curve of the embodiment of the invention 2.
Fig. 3 is the initial stage charging and discharging curve of siliceous cathode of lithium battery in the embodiment of the invention 5.
Fig. 4 is a siliceous cathode of lithium battery (a) and the contrast of the embodiment of the invention 7 metal lithium sheet negative battery (b) cycle performances in the embodiment of the invention 5.
Embodiment
Do explanation further below in conjunction with embodiment and accompanying drawing specific embodiments of the invention.
As shown in Figure 1; For siliceous cathode of lithium of the present invention prepares the process sketch map; The first step is a silicon materials storage lithium process, and preparation is the siliceous negative plate of storage lithium in advance: siliceous negative material is mixed being coated on the collector 1 with conductive agent, binding agent, this collector 1 is selected Copper Foil; Drying, preparation material pole piece 2; With this material pole piece is positive pole; Metal lithium sheet is a negative pole, and assembled battery is discharged-charging cycle with 10 ~ 1000mA/g current density between 0.01V ~ 2V; The material capacity is reached stablize continued and be discharged to 0.01V; Make lithium ion evenly be stored in the silicon materials, accomplish storage lithium step in advance, obtain the siliceous cathode of lithium sheet 3 that electrochemistry is stored up lithium in advance; , the storage lithium carried out for second step when accomplishing; It is excess deposition lithium metal 4; The siliceous negative plate of preparation excess deposition lithium metal: the above-mentioned 0.01V that is discharged to is accomplished the battery that stores up the lithium step, continue discharge with 10 ~ 1000mA/g current density, at siliceous cathode of lithium sheet surface electrochemistry excess deposition lithium metal; Lithium metal capacity to excess deposition is 0 ~ 2 times that material is stablized lithium storage content, obtains the siliceous cathode of lithium sheet of electrochemistry excess deposition lithium.
The preparation negative plate: with silicon/carbon composite is negative material; With conductive carbon black (Super P), sodium carboxymethylcellulose (CMC); butadiene-styrene rubber (SBR) is pressed mass ratio 80:8:4:8 and mixed; with the deionized water is solvent, be uniformly coated on the collector Cu paper tinsel behind the mixing pulping, in 80 ℃ vacuum drying chamber, dried 24 hours then.With the lithium metal is negative pole, and MCMB is anodal, and Celgrad 2035 is a barrier film, 1.5mol/L lithium hexafluoro phosphate (LiPF
6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio is 1:1:1) is assembled into battery for electrolyte.Battery at first discharges-charging cycle with the current density of 50mA/g active material, and voltage range is 0.01 ~ 2V, and circulation 8 circle back silicon materials capacity reach stable.The 9th circle continues to be discharged to 0.01V and stores up lithium (like the first step among Fig. 1) in advance, does not carry out the overdischarge excess deposition lithium in second step, and the siliceous cathode of lithium capacity that obtains is 1.23mAh.Taking-up contains silicon electrode after taking battery apart, promptly obtains the siliceous cathode of lithium sheet that electrochemistry is stored up lithium in advance.
Embodiment 2
The preparation negative plate: with silicon/carbon composite is negative material; With conductive carbon black (Super P), sodium carboxymethylcellulose (CMC); butadiene-styrene rubber (SBR) is pressed mass ratio 80:8:4:8 and mixed; with the deionized water is solvent, be uniformly coated on the collector Cu paper tinsel behind the mixing pulping, in 80 ℃ vacuum drying chamber, dried 24 hours then.With the lithium metal is negative pole, and MCMB is anodal, and Celgrad 2035 is a barrier film, 1.5mol/L lithium hexafluoro phosphate (LiPF
6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio is 1:1:1) is assembled into battery for electrolyte.Battery at first discharges-charging cycle with the current density of 50mA/g active material, and voltage range is 0.01 ~ 2V, and circulation 8 circle back silicon materials capacity reach stable, and it is 1.34mAh that the 8th circle is stablized lithium storage content.The 9th circle continues discharge, accomplishes continued excess deposition lithium (as shown in Figure 1) in discharge, and the setting discharge capacity is 2.68mAh, and promptly the lithium capacity of excess deposition is about 1 times that silicon materials are stablized lithium storage content, and the curve of storage lithium and excess deposition lithium is seen Fig. 2.Taking-up contains silicon electrode after taking battery apart, promptly obtains the siliceous cathode of lithium sheet that electrochemistry is stored up lithium and excess deposition lithium in advance.
The preparation negative plate: with silicon/carbon composite is negative material; With conductive carbon black (Super P), sodium carboxymethylcellulose (CMC); butadiene-styrene rubber (SBR) is pressed mass ratio 80:8:4:8 and mixed; with the deionized water is solvent, be uniformly coated on the collector Cu paper tinsel behind the mixing pulping, in 80 ℃ vacuum drying chamber, dried 24 hours then.With the lithium metal is negative pole; MCMB is anodal; Celgrad 2035 is a barrier film, two (trifluoromethane sulfonic acid acyl group) the imines lithiums (LiTFSI) of 1.5mol/L/dioxolanes (DOL)+1, and 2-dimethoxy-ethane (DME) (volume ratio is 1:1) is assembled into battery for electrolyte.Battery at first discharges-charging cycle with the current density of 50mA/g active material, and voltage range is 0.01 ~ 2V, and circulation 8 circle back silicon materials capacity reach stable, and it is 2.28mAh that the 8th circle is stablized lithium storage content.The 9th circle continues discharge, accomplishes continued excess deposition lithium (as shown in Figure 1) in discharge, and the setting discharge capacity is 4.55mAh, and promptly the lithium capacity of excess deposition is about 1 times that silicon materials are stablized lithium storage content.Taking-up contains silicon electrode after taking battery apart, promptly obtains the siliceous cathode of lithium sheet that electrochemistry is stored up lithium and excess deposition lithium in advance.
Embodiment 4
The battery assembling test: with the sulfide polymer is positive electrode; Mix by mass ratio 70:20:10 with conductive carbon black (ketjen black), Kynoar (PVDF); With N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent; Be uniformly coated on the collector Al paper tinsel after mixing pulping, oven dry obtained the sulfide polymer positive plate in 24 hours in 50 ℃ vacuum drying chamber then.
Under dry air or inert atmosphere conditions, use novel siliceous cathode of lithium among the embodiment 1, above-mentioned sulfide polymer is anodal, Celgrad 2035 is a barrier film, 1.5 mol/L lithium hexafluoro phosphate (LiPF
6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio is 1:1:1) is assembled into battery for electrolyte.
Battery is with 0.1C electric current charge and discharge cycles between 0.5 ~ 3.0V, and battery discharge capacity first is 0.8647 mAh, 30 times the circulation after, the discharge capacity of the cell conservation rate be first discharge capacity 38%, the second time discharge capacity 55%.This GND lithium excessive 42%.
Embodiment 5
The battery assembling test: with the sulfide polymer is positive electrode; Mix by mass ratio 70:20:10 with conductive carbon black (ketjen black), Kynoar (PVDF); With N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent; Be uniformly coated on the collector Al paper tinsel after mixing pulping, oven dry obtained the sulfide polymer positive plate in 24 hours in 50 ℃ vacuum drying chamber then.
Under dry air or inert atmosphere conditions, use novel siliceous cathode of lithium among the embodiment 2, above-mentioned sulfide polymer is anodal, Celgrad 2035 is a barrier film, 1.5 mol/L lithium hexafluoro phosphate (LiPF
6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio is 1:1:1) is assembled into lithium-sulfur cell for electrolyte.
Battery is with 0.1C electric current charge and discharge cycles between 1.0 ~ 3.0V.The initial stage charging and discharging curve of this lithium-sulfur cell is as shown in Figure 3, and the characteristic platform of sulfide polymer is arranged.Battery discharge capacity first is 0.8086mAh, 50 times the circulation after, the discharge capacity of the cell conservation rate be first discharge capacity 49%, the second time discharge capacity 73%, shown in Fig. 4 (a).This GND lithium excessive 231%.
Embodiment 6
The battery assembling test: with sulphur/carbon composite is positive electrode; Mix by mass ratio 80:8:2:10 with conductive carbon black Super P, gas-phase growth of carbon fibre (VGCF), Kynoar (PVDF); With N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent; Be uniformly coated on the collector Al paper tinsel after mixing pulping, oven dry obtained the sulfide polymer positive plate in 24 hours in 50 ℃ vacuum drying chamber then.
Under dry air or inert atmosphere conditions; Use novel siliceous cathode of lithium among the embodiment 3; Above-mentioned sulfide polymer is anodal; Celgrad 2035 is a barrier film, two (trifluoromethane sulfonic acid acyl group) the imines lithiums (LiTFSI) of 1.5mol/L/dioxolanes (DOL)+1, and 2-dimethoxy-ethane (DME) (volume ratio is 1:1) is assembled into lithium-sulfur cell for electrolyte.
Battery is with 0.1C electric current charge and discharge cycles between 1.0 ~ 3.0V.Battery discharge capacity first is 1.6215mAh, 10 times the circulation after, the discharge capacity of the cell conservation rate be first discharge capacity 47%, the second time discharge capacity 54%.This GND lithium excessive 181%.
Embodiment 7
Present embodiment is a comparison example.
The battery assembling test: with the sulfide polymer is positive electrode; Mix by mass ratio 70:20:10 with conductive carbon black (ketjen black), polytetrafluoroethylene (PEFT); With water is solvent; Be compressed on the collector nickel foam after mixing pulping, oven dry obtained the sulfide polymer positive plate in 24 hours in 50 ℃ vacuum drying chamber then.
Under dry air or inert atmosphere conditions, used thickness is that 1.2mm lithium sheet is a negative pole, and above-mentioned sulfide polymer is anodal, and Celgrad 2035 is a barrier film, 1.5 mol/L lithium hexafluoro phosphate (LiPF
6)/ethylene carbonate (EC)+diethyl carbonate (DEC)+methyl ethyl carbonate (EMC) (volume ratio is 1:1:1) is assembled into lithium-sulfur cell for electrolyte.
Battery is with 0.1C electric current charge and discharge cycles between 1.0 ~ 3.0V.Battery discharge capacity first is 13.8698mAh, after 50 circulations, the discharge capacity of the cell conservation rate be first discharge capacity 31%, for the second time battery capacity decays fast after 40%, 30 time of discharge capacity, cathode of lithium begins inefficacy, shown in Fig. 4 (b).This GND lithium excessive 3260%.
Although content of the present invention has been done detailed introduction through above-mentioned preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be conspicuous.Therefore, protection scope of the present invention should be limited appended claim.
Claims (5)
1. the preparation method of a siliceous cathode of lithium is characterized in that, this method comprises following concrete steps:
Step 1, preparation be the siliceous negative plate of storage lithium in advance: siliceous negative material is mixed being coated on the collector with conductive agent, binding agent, this collector is selected Copper Foil, drying, preparation material pole piece; With this material pole piece is positive pole; Metal lithium sheet is a negative pole, and assembled battery is discharged-charging cycle with 10 ~ 1000mA/g current density between 0.01V ~ 2V; The material capacity is reached stablize continued and be discharged to 0.01V; Make lithium ion evenly be stored in the silicon materials, accomplish storage lithium step in advance, obtain the siliceous cathode of lithium sheet that electrochemistry is stored up lithium in advance;
Step 2; The siliceous negative plate of preparation excess deposition lithium metal: the above-mentioned 0.01V that is discharged to is accomplished the battery that stores up the lithium step; Continue discharge with 10 ~ 1000mA/g current density; At siliceous cathode of lithium sheet surface electrochemistry excess deposition lithium metal, to the lithium metal capacity of excess deposition be 0 ~ 2 times that material is stablized lithium storage content, obtain the siliceous cathode of lithium sheet of electrochemistry excess deposition lithium.
2. like the preparation method of claims 1 described siliceous cathode of lithium, it is characterized in that: said siliceous negative material is selected to have more than in the active silicon/carbon composite of electrochemical lithium storage, silicon/nanocarbon/metal composite material, the silicon-base oxide composite material any one.
3. one kind comprises the siliceous cathode of lithium that method according to claim 1 and 2 makes; It is characterized in that; This siliceous cathode of lithium be with Copper Foil as collector, siliceous negative material is as carrier, behind full lithium ion of carrier inside storage or the full lithium of storage again at carrier surface excess deposition lithium metal.
4. a lithium-sulfur cell that comprises the siliceous cathode of lithium that method according to claim 1 and 2 makes is characterized in that this battery comprises described siliceous cathode of lithium, sulphurous materials positive pole, electrolyte, barrier film, shell.
5. lithium-sulfur cell as claimed in claim 4 is characterized in that, more than any one in described sulphurous materials selection elemental sulfur, sulphur/carbon composite, sulfide polymer, the organic polysulfide.
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