CN102496736A - All-solid-state polymer electrolyte used for lithium-sulfur secondary battery and its preparation method - Google Patents
All-solid-state polymer electrolyte used for lithium-sulfur secondary battery and its preparation method Download PDFInfo
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- CN102496736A CN102496736A CN2011104454067A CN201110445406A CN102496736A CN 102496736 A CN102496736 A CN 102496736A CN 2011104454067 A CN2011104454067 A CN 2011104454067A CN 201110445406 A CN201110445406 A CN 201110445406A CN 102496736 A CN102496736 A CN 102496736A
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Abstract
Belonging to the technical field of lithium-sulfur secondary battery preparation, the invention relates to an all-solid-state polymer electrolyte used for a lithium-sulfur secondary battery and its preparation method. Directed at the current situation that a metal lithium negative electrode is likely to generate a dendrite which can break a diaphragm so as to cause a short circuit when the liquid electrolyte or gel polymer electrolyte of a lithium-sulfur secondary battery matches with metal lithium, the invention provides an all-solid-state polymer electrolyte used for a lithium-sulfur secondary battery. The electrolyte comprises PEO (polyethylene oxide), a Li4Ti5O12 particle and a lithium salt, which can be LiClO4, LiPF6, LiBF4, LiCF3SO3 or LiTFSI. At a temperature of 30DEG C, the electrolyte has electric conductivity greater than 10<-4>S/cm, which is far higher than the electric conductivity of 10<-6>-10<-7>S/cm of PEO/a lithium salt at a temperature of 30DEG C. In a lithium-sulfur secondary battery, the electrolyte can serve both as an electrolyte and a diaphragm, and the double functions can substantially enhance the utilization rate and circulation stability of a positive active material.
Description
Technical field
The present invention relates to lithium-sulfur rechargeable battery with full solid state polymer electrolyte, belong to lithium-sulfur rechargeable battery manufacturing technology field.
Background technology
Because lithium rechargeable battery has little, the in light weight and specific energy advantages of higher of volume; In the portable consumer electronic product, occupy dominant position; But pressing for, the development of electric automobile develops the more secondary cell of high-energy-density; And lithium-sulfur cell has specific energy height (theoretical specific energy is up to 2600Wh/Kg), cost is low and advantage such as environmental friendliness, is one of ideal power of electric automobile.Yet the room-temperature conductivity of elemental sulfur has only 5 * 10
-30S/cm is near electronic isolation; The sulfur electrode cycle performance is poor, and intermediate product is prone in organic electrolyte, dissolve, and these defectives have suppressed the application of lithium-sulfur cell.
These defectives to lithium-sulfur cell; The researcher mainly improves the performance of lithium-sulfur cell from two aspects: the one, change existing electrolyte of lithium-ion secondary battery prescription; Add various functional additive, reduce the solubility of many sulphur product in electrolyte, improve cycle performance.Discover many sulphur product reactivity and invertibity raising in the electrolyte that is made into dioxolanes (DOL), dimethoxy-ethane (DME), tetraethyleneglycol dimethyl ether (TEGDME) equal solvent, battery performance improves.Chinese patent ZL 03154619.6 is described in also when lithium-sulfur cell and comprises when having the anionic salt of acid imide as electrolyte, and the utilance of sulphur is improved, and cycle life and flash-over characteristic such as discharge capacity and discharge platform also improve.The 2nd, the modification that sulphur is anodal mainly is to adsorb sulphur with various material with carbon elements, reaches to improve sulphur positive electrical conductance, reduces the purpose of the dissolving of many sulphur product.Discharge and recharge reversible specific capacity under the lithium-sulfur cell room temperature that the sulfenyl positive electrode of Chinese patent ZL 201010255445.6 usefulness carbon nanotubess and lithium anode are formed and reach 697mAh/g, and excellent cycle performance is arranged.
But at present; Because when liquid electrolysis system or gel polymer electrolyte and lithium metal coupling; Lithium anode is easy to generate dendrite, breaks through barrier film and the situation of short circuit, and adopts the lithium-sulfur cell of common electrolyte; The utilance and the cyclical stability of positive active material are poor, cause the limited use of lithium-sulfur cell.
Summary of the invention
First purpose of the present invention is, to a kind of new electrolyte of above-mentioned proposition, full solid state polymer electrolyte.This electrolyte in lithium-sulfur rechargeable battery not only as electrolyte but also as the double action of barrier film.
The object of the invention is realized through following technical proposals:
Full solid state polymer electrolyte of the present invention comprises PEO (PEO), Li
4Ti
5O
12Particle and lithium salts; Wherein the mol ratio of EO base is 1: 2～32 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.01～0.25: 1; Said lithium salts is LiClO
4, LiPF
6, LiBF
4, LiCF
3SO
3Or LiTFSI.
The Li that adds in the full solid state polymer electrolyte of the present invention
4Ti
5O
12Particle is an ion conductor, Li
+Diffusion coefficient is also higher than carbon negative pole material, when improving the full solid state polymer electrolyte conductivity, has also increased carrier concentration, and the full solid state polymer electrolyte conductivity is greater than 10 in the time of 30 ℃
-4S/cm is far above 30 ℃ of conductivity 10 of PEO/ lithium salts
-6～10
-7S/cm.
As the preferred scheme of the present invention, Li
4Ti
5O
12The particle diameter of particle is 0.05～1um.
As the preferred scheme of the present invention, the mol ratio of EO base is 1: 6～20 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.05～0.20: 1.
What choosing was more arranged is that the mol ratio of EO base is 1: 8～16 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.1～0.15: 1.
The preparation method of full solid state polymer electrolyte of the present invention may further comprise the steps:
(1) with lithium salts and organic solvent mixing and stirring, PEO (PEO) powder is added continue to be stirred in the above-mentioned mixed liquor evenly then, wherein the mol ratio of EO base is 1: 2～32 among lithium salts and the PEO, preferred 1: 6～20, more preferably 1: 8～16; The mass ratio of PEO and solvent 1: 10～100, preferred 1: 20～90, more preferably 1: 20～50.
(2) with Li
4Ti
5O
12Particle mixes with organic solvent, wherein Li
4Ti
5O
12Particle diameter is 0.05～1um (preferred 0.05～0.5um; More preferably 0.05～0.1um) with the mass ratio of PEO be 0.01～0.25: 1 (preferred 0.05～0.20: 1; More preferably 0.1～0.15: 1); Speed with 200～500r/min behind sonic oscillation 30～60min is stirred to evenly, leaves standstill 5～10min.
(3) mixture with step (1) and step (2) mixes to evenly, is poured into mould, down dry 1～3 day aftershaping of room temperature condition, and the demoulding gets product.
Solvent described in the said method is acetonitrile or acetone, or both mixed solvents; Described PEO molecular weight is 10～600,000; Described lithium salts is LiClO
4, LiPF
6, LiBF
4, LiCF
3SO
3Or LiTFSI.
Second purpose of the present invention is to provide all solid state lithium-sulfur cell with cyclical stability preferably that is prepared from above-mentioned full solid state polymer electrolyte and preparation method thereof.
All solid lithium of the present invention-sulphur battery comprises above-mentioned full solid state polymer electrolyte, and positive electrode and negative material, said positive electrode are the lithium-sulfur cell positive electrode of studying in the prior art.Specifically be the material with carbon element S-C material that has adsorbed sulphur, such as adopting one Chinese patent application 200910085136.6 disclosed elemental sulfur composite material used by lithium secondary battery S-C materials.The negative material of described all solid state lithium-sulfur cell is a lithium metal.
Compared with prior art, the present invention has the following advantages:
1, full solid state polymer electrolyte of the present invention can play the double action of electrolyte and barrier film simultaneously, can reach to reduce cost, and reduces the purpose of the technological process of production.
2, full solid state polymer electrolyte of the present invention can mate with lithium metal, and when having avoided with liquid electrolysis system or gel polymer electrolyte and lithium metal coupling, lithium anode is easy to generate dendrite, breaks through barrier film and the situation of short circuit.
3, lithium-sulfur cell full solid state polymer electrolyte of the present invention is compared with the lithium-sulfur cell that adopts common electrolyte, and the utilance and the cyclical stability of positive active material are greatly improved.
4, full solid state polymer electrolyte manufacture craft of the present invention is simple, and is not harsh to operation and environmental requirement, for technology production provides simple and easy to do condition.
5, the Li that adds in the full solid state polymer electrolyte of the present invention
4Ti
5O
12Particle is an ion conductor, Li
+Diffusion coefficient is also higher than carbon negative pole material, when improving the full solid state polymer electrolyte conductivity, has also increased carrier concentration, and the full solid state polymer electrolyte conductivity is greater than 10 in the time of 30 ℃
-4S/cm is far above 30 ℃ of conductivity 10 of PEO/ lithium salts
-6～10
-7S/cm.
Description of drawings
Fig. 1 when adopting the prepared full solid state polymer electrolyte of the embodiment of the invention 1 80 ℃ as all solid lithium-sulphur cell electrolyte, discharge curve first under the 50mA/g current density.
Fig. 2 when adopting the prepared full solid state polymer electrolyte of the embodiment of the invention 1 80 ℃ as all solid lithium-sulphur cell electrolyte, cycle performance of battery figure under the 50mA/g current density.
Embodiment
Full solid state polymer electrolyte of the present invention is by PEO (PEO), Li
4Ti
5O
12Particle and lithium salts are formed; Wherein the mol ratio of EO base is 1: 2～32 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.01～0.25: 1; Said lithium salts is LiClO
4, LiPF
6, LiBF
4, LiCF
3SO
3Or LiTFSI.
Li
4Ti
5O
12Be the composite oxides that a kind of lithium metal and Titanium are formed, be cubic system, belong to AB
2X
4Series, wherein O2
-Be positioned at the 32e position, 3/4 Li
+Be positioned at the 8a position, remaining Li
+And Ti
4+Be positioned at the 16d position.Li
4Ti
5O
12Itself can ionization not produce Li
+, general as negative pole in lithium ion battery, the chemical process in lithium ion battery can be represented
The Li that adds in the full solid state polymer electrolyte of the present invention
4Ti
5O
12Particle is an ion conductor, Li
+Diffusion coefficient is also higher than carbon negative pole material, when improving the full solid state polymer electrolyte conductivity, has also increased carrier concentration, and the full solid state polymer electrolyte conductivity is greater than 10 in the time of 30 ℃
-4S/cm is far above 30 ℃ of conductivity 10 of PEO/ lithium salts
-6～10
-7S/cm.
As the preferred scheme of the present invention, Li
4Ti
5O
12The particle diameter of particle is 0.05～1um.
As the preferred scheme of the present invention, the mol ratio of EO base is 1: 6～20 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.05～0.20: 1.
What choosing was more arranged is that the mol ratio of EO base is 1: 8～16 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.1～0.15: 1.
The preparation method of full solid state polymer electrolyte of the present invention may further comprise the steps:
(1) with lithium salts and organic solvent mixing and stirring, PEO (PEO) powder is added continue to be stirred in the above-mentioned mixed liquor evenly then, wherein the mol ratio of EO base is 1: 2～32 among lithium salts and the PEO, preferred 1: 6～20, more preferably 1: 8～16; The mass ratio of PEO and solvent 1: 10～100, preferred 1: 20～90, more preferably 1: 20～50.
(2) with Li
4Ti
5O
12Particle mixes with organic solvent, wherein Li
4Ti
5O
12Particle diameter is 0.05～1um (preferred 0.05～0.5um; More preferably 0.05～0.1um) with the mass ratio of PEO be 0.01～0.25: 1 (preferred 0.05～0.20: 1; More preferably 0.1～0.15: 1); Speed with 200～500r/min behind sonic oscillation 30～60min is stirred to evenly, leaves standstill 5～10min.
(3) mixture with step (1) and step (2) mixes to evenly, is poured into mould, down dry 1～3 day aftershaping of room temperature condition, and the demoulding gets product.
Solvent described in the said method is acetonitrile or acetone, or both mixed solvents; Described PEO molecular weight is 10～600,000; Described lithium salts is LiClO
4, LiPF
6, LiBF
4, LiCF
3SO
3Or LiTFSI.
Second purpose of the present invention is to provide all solid state lithium-sulfur cell with cyclical stability preferably that is prepared from above-mentioned full solid state polymer electrolyte and preparation method thereof.
All solid lithium of the present invention-sulphur battery comprises above-mentioned full solid state polymer electrolyte, and positive electrode and negative material, said positive electrode are the lithium-sulfur cell positive electrode of studying in the prior art.Specifically be the material with carbon element S-C material that has adsorbed sulphur, such as adopting one Chinese patent application 200910085136.6 disclosed elemental sulfur composite material used by lithium secondary battery S-C materials.The negative material of described all solid state lithium-sulfur cell is a lithium metal.
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but execution mode of the present invention is not limited thereto, also comprises the combination in any between embodiment.
Embodiment 1
The full solid state polymer electrolyte of this execution mode is by LiCF
3SO
3, PEO (PEO) and Li
4Ti
5O
12Particle is formed, wherein LiCF
3SO
3The mol ratio basic with the EO of PEO is 1: 16, Li
4Ti
5O
12The mass ratio of particle and PEO is 0.1: 1.
Through the conductivity of AC impedence method mensuration full solid state polymer electrolyte, the frequency range of test is 1～100kHz, and amplitude is 10mV.The conductivity δ of full solid state polymer electrolyte=L/ (S * R); L is the thickness of full solid state polymer electrolyte; S is the area of full solid state polymer electrolyte, and R is this volume resistance of full solid state polymer electrolyte, and conductivity is 2.5 * 10 when 80 ℃ of full solid state polymer electrolytes of test
-3S/cm.
The full solid state polymer electrolyte of being invented in this execution mode must be used in the preparation lithium-sulfur cell; The preparation technology of lithium-sulfur cell is following: full solid state polymer electrolyte is pressed sulphur positive electrode (70%S-C successively; 20%Super-P 10%LA132), full solid state polymer electrolyte and negative material lithium metal form 2032 all solid state button cells, discharges and recharges under 80 ℃ of 50mA/g; Discharge capacity is 1235.8mAh/g first, and the utilance of sulphur is 73.9%.Two tangible discharge platforms have appearred on discharge curve, respectively about 2.4V and 2.1V.50 times circulation back specific discharge capacity also remains on 936.4mAh/g, has demonstrated good cyclical stability.
Embodiment 2
The full solid state polymer electrolyte of this execution mode is by LiTFSI, PEO (PEO) and Li
4Ti
5O
12Particle is formed, and wherein the mol ratio of the EO of LiTFSI and PEO base is 1: 6, Li
4Ti
5O
12The mass ratio of particle and PEO is 0.05: 1.Conductivity is 3.2 * 10 when 90 ℃ of full solid state polymer electrolytes of test
-3S/cm.
The full solid state polymer electrolyte of being invented in this execution mode must be used in the preparation lithium-sulfur cell; The preparation technology of lithium-sulfur cell is following: full solid state polymer electrolyte is pressed sulphur positive electrode (70%S-C successively; 20%Super-P; 10%LA132), full solid state polymer electrolyte and negative material lithium metal form 2032 all solid state button cells, under 90 ℃ of 50mA/g, discharges and recharges, discharge capacity is 1596.4mAh/g first; The utilance of sulphur is 95.5%, and circulating, specific discharge capacity is 982.1mAh/g after 50 times.
Embodiment 3
The full solid state polymer electrolyte of this execution mode is by LiPF
6, PEO (PEO) and Li
4Ti
5O
12Particle is formed, wherein LiPF
6The mol ratio basic with the EO of PEO is 1: 6, Li
4Ti
5O
12The mass ratio of particle and PEO is 0.01: 1.Conductivity is 1.3 * 10 when 70 ℃ of full solid state polymer electrolytes of test
-3S/cm.
The full solid state polymer electrolyte of being invented in this execution mode must be used in the preparation lithium-sulfur cell; The preparation technology of lithium-sulfur cell is following: full solid state polymer electrolyte is pressed sulphur positive electrode (70%S-C successively; 20%Super-P; 10%LA132), full solid state polymer electrolyte and negative material lithium metal form 2032 all solid state button cells, under 70 ℃ of 50mA/g, discharges and recharges, discharge capacity is 1147.6mAh/g first; The utilance of sulphur is 68.6%, and circulating, specific discharge capacity is 820.1mAh/g after 50 times.
Embodiment 4
The full solid state polymer electrolyte of this execution mode is by LiClO
4, PEO (PEO) and Li
4Ti
5O
12Particle is formed, wherein LiClO
4The mol ratio basic with the EO of PEO is 1: 8, Li
4Ti
5O
12The mass ratio of particle and PEO is 0.20: 1.Conductivity is 7.4 * 10 when 60 ℃ of full solid state polymer electrolytes of test
-4S/cm.
The full solid state polymer electrolyte of being invented in this execution mode must be used in the preparation lithium-sulfur cell; The preparation technology of lithium-sulfur cell is following: full solid state polymer electrolyte is pressed sulphur positive electrode (60%S-C successively; 30%Super-P; 10%LA132), full solid state polymer electrolyte and negative material lithium metal form 2032 all solid state button cells, under 60 ℃ of 50mA/g, discharges and recharges, discharge capacity is 1015mAh/g first; The utilance of sulphur is 60.7%, and circulating, specific discharge capacity is 734.7mAh/g after 50 times.
Embodiment 5
The full solid state polymer electrolyte of this execution mode is by LiTFSI, PEO (PEO) and Li
4Ti
5O
12Particle is formed, and wherein the mol ratio of the EO of LiTFSI and PEO base is 1: 10, Li
4Ti
5O
12The mass ratio of particle and PEO is 0.25: 1.Conductivity is 5.1 * 10 when 50 ℃ of full solid state polymer electrolytes of test
-3S/cm.
The full solid state polymer electrolyte of being invented in this execution mode must be used in the preparation lithium-sulfur cell; The preparation technology of lithium-sulfur cell is following: full solid state polymer electrolyte is pressed sulphur positive electrode (60%S-C successively; 30%Super-P; 10%LA132), full solid state polymer electrolyte and negative material lithium metal form 2032 all solid state button cells, under 50 ℃ of 20mA/g, discharges and recharges, discharge capacity is 1085.4mAh/g first; The utilance of sulphur is 64.9%, and circulating, specific discharge capacity is 792.3mAh/g after 50 times.
Embodiment 6
The full solid state polymer electrolyte of this execution mode is by LiTFSI, PEO (PEO) and Li
4Ti
5O
12Particle is formed, and wherein the mol ratio of the EO of LiTFSI and PEO base is 1: 16, Li
4Ti
5O
12The mass ratio of particle and PEO is 0.15: 1.Conductivity is 2.7 * 10 when 80 ℃ of full solid state polymer electrolytes of test
-3S/cm.
The full solid state polymer electrolyte of being invented in this execution mode must be used in the preparation lithium-sulfur cell; The preparation technology of lithium-sulfur cell is following: full solid state polymer electrolyte is pressed sulphur positive electrode (70%S-C successively; 20%Super-P; 10%LA132), full solid state polymer electrolyte and negative material lithium metal form 2032 all solid state button cells, under 80 ℃ of 20mA/g, discharges and recharges, discharge capacity is 1631.2mAh/g first; The utilance of sulphur is 97.6%, and circulating, specific discharge capacity is 1012.1mAh/g after 50 times.
Claims (10)
1. lithium-sulfur rechargeable battery is used full solid state polymer electrolyte, it is characterized in that: by PEO, Li
4Ti
5O
12Particle and lithium salts are formed; Wherein the mol ratio of EO base is 1: 2～32 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.01～0.25: 1; Said lithium salts is LiClO
4, LiPF
6, LiBF
4, LiCF
3SO
3Or LiTFSI.
2. lithium-sulfur rechargeable battery according to claim 1 is used full solid state polymer electrolyte, it is characterized in that: Li
4Ti
5O
12The particle diameter of particle is 0.05～1um.
3. lithium-sulfur rechargeable battery according to claim 1 is used full solid state polymer electrolyte, it is characterized in that: the mol ratio of EO base is 1: 6～20 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.05～0.20: 1.
4. lithium-sulfur rechargeable battery according to claim 3 is used full solid state polymer electrolyte, it is characterized in that: the mol ratio of EO base is 1: 8～16 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.1～0.15: 1.
5. prepare the method for the described lithium-sulfur rechargeable battery of claim 1, it is characterized in that: may further comprise the steps with full solid state polymer electrolyte:
(1) with lithium salts and organic solvent mixing and stirring, the PEO powder is added continue to be stirred in the above-mentioned mixed liquor evenly then, wherein the mol ratio of EO base is 1: 2～32 among lithium salts and the PEO; The mass ratio of PEO and solvent 1: 10～100;
(2) with Li
4Ti
5O
12Particle mixes with organic solvent, wherein Li
4Ti
5O
12Particle diameter is that the mass ratio of 0.05～1um and PEO is 0.01～0.25: 1, stirs;
(3) with step (1) and step (2) gained mixing of materials, stir, be poured into mould, room temperature condition is down dry, the demoulding promptly gets.
6. according to the said method for preparing lithium-sulfur rechargeable battery with full solid state polymer electrolyte of claim 5, it is characterized in that: described solvent is at least a in acetonitrile, the acetone.
7. according to the said method for preparing lithium-sulfur rechargeable battery with full solid state polymer electrolyte of claim 6, it is characterized in that: described PEO molecular weight is 10～600,000; Described lithium salts is LiClO
4, LiPF
6, LiBF
4, LiCF
3SO
3Or LiTFSI.
8. according to each said method for preparing full solid state polymer electrolyte of claim 5～7, it is characterized in that: Li
4Ti
5O
12The particle diameter of particle is 0.05～1um.
9. lithium-sulfur rechargeable battery according to claim 8 is used full solid state polymer electrolyte, it is characterized in that: the mol ratio of EO base is 1: 6～20 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.05～0.20: 1; Further preferred, the mol ratio of EO base is 1: 8～16 among lithium salts and the PEO; Li
4Ti
5O
12The mass ratio of particle and PEO is 0.1～0.15: 1.
10. lithium-sulfur rechargeable battery is characterized in that: comprise that each described lithium-sulfur rechargeable battery of positive electrode, negative material and claim 1～5 uses full solid state polymer electrolyte.
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| CN103972580A (en) * | 2013-02-06 | 2014-08-06 | 苏州宝时得电动工具有限公司 | Lithium sulfur battery |
| CN104341764A (en) * | 2014-09-12 | 2015-02-11 | 太原科技大学 | Material applicable to anode bonding and preparation method thereof |
| CN104508899A (en) * | 2012-08-09 | 2015-04-08 | 丰田自动车株式会社 | All-solid-state battery and method for manufacturing same |
| CN105409032A (en) * | 2013-06-21 | 2016-03-16 | 魁北克电力公司 | All-solid-state lithium-sulphur electrochemical cells and production methods thereof |
| CN109336046A (en) * | 2018-11-20 | 2019-02-15 | 太原科技大学 | A kind of preparation process for the PEG group composite solid polymer electrolyte applied in anode linkage |
| CN109768323A (en) * | 2018-12-05 | 2019-05-17 | 湖州天丰电源有限公司 | A kind of all solid lithium metal-sulfur cell and preparation method thereof |
| US10490848B2 (en) | 2013-10-18 | 2019-11-26 | Cornell University | Solid polymer electrolyte composition |
| CN113964454A (en) * | 2021-10-25 | 2022-01-21 | 合肥国轩高科动力能源有限公司 | High-energy-density non-negative lithium battery |
| CN114512708A (en) * | 2022-01-26 | 2022-05-17 | 浙江地坤键新能源科技有限公司 | Preparation method and application of lithium ion composite solid electrolyte |
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