CN109786869B - Application of polymer containing hindered amine structure in secondary lithium battery - Google Patents

Application of polymer containing hindered amine structure in secondary lithium battery Download PDF

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CN109786869B
CN109786869B CN201811554692.9A CN201811554692A CN109786869B CN 109786869 B CN109786869 B CN 109786869B CN 201811554692 A CN201811554692 A CN 201811554692A CN 109786869 B CN109786869 B CN 109786869B
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carbonate
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CN109786869A (en
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崔光磊
张焕瑞
马月
董甜甜
徐红霞
王鹏
邹振宇
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Zhongke Shenlan Huize New Energy Qingdao Co ltd
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • H—ELECTRICITY
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    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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Abstract

The invention relates to an application of a polymer containing a hindered amine structure in a secondary lithium battery. The polymer contains a hindered amine structural unit, can capture oxygen radical species generated in the operation of the battery, quench hydroperoxide, capture heavy metal and quench singlet oxygen generated in the operation of the battery, and therefore, the polymer is beneficial to inhibiting side reaction of a positive electrode interface, reducing oxygen-containing waste gas and improving the coulombic efficiency and long cycle performance of the battery.

Description

Application of polymer containing hindered amine structure in secondary lithium battery
Technical Field
The invention relates to the field of secondary lithium batteries, in particular to application of a polymer containing a hindered amine structure in a secondary lithium battery.
Background
Lithium ion batteries have been developed in the fields of mobile devices, electric vehicles, smart grids, and the like, due to the advantages of high energy density and good reliability. However, several serious battery burn events that have recently occurred with the tesla Model S vehicle (battery pack with NCA as the positive active material) have sounded the alarm for the commercial application of lithium batteries. It is reported in the literature that thermal runaway of batteries is closely related to chemical shuttling of oxygen (especially singlet oxygen) produced by the positive electrode material without significant short-circuiting of the battery (Joule 2018, doi 10.1016/j.joule.2018.06.015. Specifically, the high-activity singlet oxygen generated from the cathode material not only causes decomposition of the electrolyte but also diffuses to the anode interface to cause a severe side reaction and release a large amount of heat, thereby inducing thermal runaway of the battery.
In order to avoid the risk of thermal runaway of the battery, many beneficial attempts have been made by scientists in the development of flame retardant electrolytes and in the research of novel solid polymer electrolytes. For example, the recent task group Cao Yuliang at Wuhan university developed a nonflammable electrolyte system triethyl phosphate/LiFSI (molar ratio = 2:1). The 18650 soft package battery assembled by the system not only shows high coulombic efficiency (99.7%) and stable cycle performance (the capacity retention rate is still 90% after 50 cycles of cycle), but also shows excellent safety performance after safety tests such as needling, short circuit, weight impact and the like (Nature Energy 2018, DOI; the subject group prepared LiCoO by in-situ polymerization of vinylene carbonate under the initiation of azobisisobutyronitrile 2 the/Li button cell not only exhibits superior rate performance and stable cycling performance (adv.sci.2017, 4,1600377), but also exhibits excellent safety. Although these methods can effectively improve the electrochemical and safety performance of the battery, the severe side reactions at the positive electrode interface caused by the highly reactive oxygen species and the risk of thermal runaway induced by the side reactions are not fundamentally inhibited or solved. In view of the urgent need of high-safety and high-energy density lithium batteries, a solution for effectively reducing the side reactions caused by active oxygen species is developed, which is of great significance for the commercial application of high-safety and high-energy density lithium batteries.
In summary, how to avoid the thermal runaway problem of the lithium ion battery has become one of the hot spots of research in the scientific community. The literature reports that severe side reactions and large exotherms due to reactive oxygen species are one of the causes of thermal runaway in batteries. Although scientists have actively pursued many attempts to avoid thermal runaway in batteries, the severe side reactions at the positive electrode interface due to highly reactive oxygen species are still not fundamentally inhibited or addressed. Therefore, the development of a material system (polymer electrolyte or positive electrode coating) that effectively suppresses the side reactions caused by the active oxygen species is of great importance for the commercial application of secondary lithium batteries.
Disclosure of Invention
The invention aims to provide an application of a polymer containing a hindered amine structure in a secondary lithium battery.
In order to achieve the purpose, the invention adopts the technical scheme that: the application of the polymer containing the hindered amine structure in a secondary lithium battery is provided, and the polymer structure contains a hindered amine structural unit.
The polymer containing the hindered amine structure is applied to a secondary lithium battery, and can capture oxygen radical species generated in the operation of the battery, quench hydroperoxide, capture heavy metal and quench singlet oxygen generated in the operation of the battery, so that the polymer is beneficial to inhibiting side reaction of a positive electrode interface, reducing oxygen-containing waste gas and improving the coulombic efficiency and the cycle performance of the battery.
The polymer containing the hindered amine structure is applied to a secondary lithium battery, and the structure of the polymer is shown as a general formula 1:
Figure GDA0003152906160000021
wherein m is 0-2000 and n is 1-2000; a. The 1 、A 2 Each independently selected from H, COOH, CN, CONH 2 An alkoxycarbonyl group not more than eighteen carbon atoms, a perfluoroalkoxycarbonyl group not more than eighteen carbon atoms, an alkylaminoacyl group not more than eighteen carbon atoms, an alkyl group not more than eighteen carbon atoms, an alkoxy group not more than eighteen carbon atoms, an aryl group not more than eighteen carbon atoms,
Figure GDA0003152906160000031
(a takes a value of 1 to 250),
Figure GDA0003152906160000032
(the value of b is 1 to 250),
Figure GDA0003152906160000033
(c takes a value of 1 to 250),
Figure GDA0003152906160000034
(B is NH, O, OCH 2 ；E - Is PF 6 ˉ，BF 4 ˉ，TFSIˉ，FSIˉ，CH 3 OSO 3 ˉ)，
Figure GDA0003152906160000035
Figure GDA0003152906160000036
(B is NH, O, OCH 2 )，
Figure GDA0003152906160000037
(v takes on a value of 1-4); b is selected from O, NH, OCH 2 (ii) a The value of W is 0-4; x is selected from H, oxygen free radical, alkoxy under octadecyl, alkyl under octadecyl, acyl under octadecyl; y is selected from H, methyl, methoxy, CN, F; z is selected from H, methyl, trifluoromethyl, chloromethyl and cyanomethyl.
The polymer containing the hindered amine structure is applied to a secondary lithium battery, and the lithium battery comprises a negative electrode, a positive electrode, a diaphragm arranged between the negative electrode and the positive electrode and a non-aqueous electrolyte; the positive electrode comprises a positive active material, a binder, a conductive carbon material and a current collector; the polymer or the nonaqueous electrolyte coated on the surface of the lithium battery positive electrode contains the polymer or the positive electrode binder contains the polymer.
The active material of the negative electrode is one or more of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, carbon-silicon composite material, carbon-germanium composite material, carbon-tin composite material, antimony oxide, antimony-carbon composite material, tin-antimony composite material, lithium titanium oxide and lithium metal nitride.
The active material of the positive electrode is one or more of lithium cobaltate, lithium manganese iron phosphate, lithium manganate, lithium nickel manganese oxide, lithium-rich manganese base, ternary material, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate and lithium manganese oxide; the binder of the anode contains one or more polymers, wherein the polymers account for 0.001-20% of the anode material
The diaphragm material is one of a cellulose non-woven membrane, a seaweed fiber non-woven membrane, an aramid fiber non-woven membrane, a polyarylsulfone amide non-woven membrane, a polypropylene non-woven membrane, glass fiber, a polyethylene terephthalate film and a polyimide non-woven membrane.
The non-aqueous electrolyte comprises lithium salt, an organic matrix and an inorganic lithium ion conductor, wherein the polymer accounts for 0-60% of the total weight of the non-aqueous electrolyte.
The lithium salt is lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoro (CF) 3 SO 3 Li), lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) and lithium bis (fluoro) sulfonyl imide (LiFSI), wherein the lithium salt accounts for 0-40% of the non-aqueous electrolyte.
The organic matrix is one or a mixture of more of ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, diethyl carbonate, succinonitrile, ethanedinitrile, fluoroethylene carbonate, tetraethylene glycol dimethyl ether, sulfolane, polyethylene carbonate, polyacrylonitrile, polymethacrylate, polyethylene oxide, polyethylene carbonate, polypropylene carbonate and the like, and accounts for 0-70% of the total weight of the electrolyte.
The inorganic lithium ion conductor is Li 3a La (2/3)-a TiO 3 (0.04<a<0.14)、Li 3+a X a Y 1-a O 4 (X＝Si、Sc、Ge、Ti；Y＝P、As、V、Cr，0<a<1)、LiZr 2 (PO 4 ) 3 、Li 7 La 3 Zr 2 O 12 、Li 1+a Al a Ti 2-a (PO 4 ) 3 (0<a<2)、Li 1+a Al a Ge 2-a (PO 4 ) 3 (0<a<2)、Li 3 OCl、Li 3 OCl 0.5 Br 0.5 、Li 10 GeP 2 S 12 、Li 14 Zn(GeO 4 ) 4 、Li 5 La 3 M 2 O 12 (M＝Ta、Nb)、Li 5.5 La 3 Nb 1.75 In 0.25 O 12 、Li 3 N-LiX(X＝Cl、Br、I)、Li 9-na M a N 2 Cl 3 (M＝Na、K、Rb、Cs、Mg、Al，0<a<9，0<n<4)、3Li 3 N-MI(X＝Li、Na、K)、LiPON、Li 2 S-M a S b (M＝Al、Si、P，0<a<3，0<b<6)、Li 6 PS 5 One or more of X (X = F, cl, br and I), and the inorganic lithium ion conductor accounts for 0-99.9% of the total mass of the electrolyte.
The polymer for preventing thermal runaway is applied to a secondary lithium metal battery, and a positive electrode coated with the polymer is prepared by the following method: dissolving a polymer in a solvent to form a uniform solution, spin-coating the solution containing the polymer on the surface of the positive electrode, and then drying the solution in a vacuum drying oven at 80 ℃ to obtain the positive electrode containing the polymer coating, wherein the thickness of the coating is 0.001-50 mu m.
In the solution containing the polymer, a solvent for dissolving the polymer is one or more of dichloromethane, chloroform, 1,4-dioxane, ethylene glycol dimethyl ether, acetone, acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, diethyl sulfite, tetrahydrofuran, 1,2-dichloroethane, ethyl acetate, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the polymer accounts for 10-80% of the total weight of the solution.
The invention relates to an application of a polymer containing a hindered amine structure in a secondary lithium battery, which has the following advantages:
1. the polymer contains more lithium ion conducting groups and has higher lithium ion conductivity;
2. the polymer contains a hindered amine structure, can capture oxygen radical species generated in the operation of the battery, quench hydroperoxide, capture heavy metal and quench singlet oxygen generated in the operation of the battery, and therefore, the polymer is beneficial to inhibiting side reaction of a positive electrode interface, reducing oxygen-containing waste gas and improving the coulombic efficiency and the cycle performance of the battery.
The technical scheme of the invention is simple and convenient to operate, and has stronger innovativeness and important application value. The scheme can be applied to high-voltage lithium batteries, solid-state lithium batteries (including lithium-sulfur batteries) and other secondary high-energy lithium batteries.
Drawings
Fig. 1 long cycle performance at room temperature of 1.0C for the assembled cell of example 1.
Figure 2 long cycle performance at room temperature of 1.0C for the assembled cell of example 2.
Fig. 3 long cycle performance at room temperature of 0.2C for the assembled cell of example 3.
Figure 4 long cycle performance of 0.5C at room temperature for assembled cells of example 4.
Figure 5 long cycle performance of 0.5C at room temperature for the assembled cell of example 5.
Figure 6 long cycle performance of 0.5C at room temperature for assembled cells of example 6.
Figure 7 long cycle performance of 0.5C at room temperature for the assembled cell of example 7.
Figure 8 long cycle performance of 0.1C at room temperature for the assembled cell of example 8.
Figure 9 long cycle performance of 0.1C at room temperature for the assembled cell of example 9.
Figure 10 long cycle performance of 0.5C at room temperature for the assembled cell of example 10.
Figure 11 first cycle oxygen production of 0.5C at room temperature for an assembled cell of example 11.
Fig. 12 the 1C first cycle carbon dioxide production at 60 degrees celsius for the assembled cell of example 12.
Figure 13 first cycle carbon monoxide yield at room temperature of 1C for assembled cells of example 13.
Fig. 14 long cycle performance at 60 degrees for the assembled cell of example 15 at 2C.
Detailed Description
Example 1
In a glove box, polymer P1 was put
Figure GDA0003152906160000051
A chloroform solution (25 wt%) of (n = 80) was coated on the positive electrode, and after standing and drying, a positive electrode containing a polymer protective layer (thickness of about 1 nm) was obtained. The anode containing the protective layer is used in a lithium ion battery, and under the charge and discharge of 1.0C, after the battery is cycled for 100 circles, the specific discharge capacity is 141mAh/g, and the efficiency is stabilized to be more than 99%.
Figure GDA0003152906160000052
Example 2
In a glove box, polymer P2
Figure GDA0003152906160000061
(n =40,20wt%) was coated on the positive electrode, and left to dry, to obtain a positive electrode containing a polymer protective layer (thickness of about 15 μm). The anode containing the protective layer is used in a lithium ion battery, and under the charge and discharge of 1.0C, after the battery is cycled for 100 circles, the specific discharge capacity is still maintained at 126mAh/g.
Figure GDA0003152906160000062
Example 3
In the glove box, polymer P3 was put in
Figure GDA0003152906160000063
A solution (50 wt%) of N, N-dimethylformamide (N = 5) was coated on the positive electrode, and left to dry. The positive electrode containing the polymer protective layer (with the thickness of about 50 mu m) is used in the lithium-sulfur battery, and under the charge and discharge of 0.2C, after the battery is cycled for 200 circles, the specific discharge capacity is still maintained at 891mAh/g, and the efficiency is maintained at more than 99%.
Figure GDA0003152906160000064
Example 4
In a glove box, block copolymer P4
Figure GDA0003152906160000071
(m =100, n = 80) was mixed and dissolved in dimethyl sulfoxide with liddob (mass ratio = 10) and then an electrolyte composite separator was prepared using glass fiber as a support material, and applied to a carbon-tin composite/ternary material battery, as can be seen from fig. 4, the battery had a capacity retention rate of 95% after 100 cycles at 0.5C.
Figure GDA0003152906160000072
Example 5
In the glove box, polymer P5 was added
Figure GDA0003152906160000073
With Li 7 La 3 Zr 2 O 12 Mixing and dissolving the materials in dimethyl sulfoxide (30 wt%), tabletting to obtain solid electrolyte, and assembling the solid electrolyte with positive and negative electrode materials.
As shown in fig. 5, the capacity retention ratio of the battery after 100 cycles of 0.5C was 93.5%.
Figure GDA0003152906160000074
Example 6
In a glove box, oligomer P6 was added
Figure GDA0003152906160000081
(N =3, m = 3) was dissolved in N-methylpyrrolidone (20 wt%), coated on the positive electrode, and left to dry. The battery was assembled and tested for its performance, as shown in fig. 6, the battery had excellent cycle performance, and the capacity of 140mAh/g was maintained after 50 cycles at 0.5C.
Figure GDA0003152906160000082
Example 7
In the glove box, polymer P7 was added
Figure GDA0003152906160000083
(n = 10) after dimethyl sulfoxide (25 wt%) was dissolved, the solution was coated on a positive electrode, and left to dry. The battery is assembled and the performance of the corresponding battery is tested, and as shown in figure 7, the battery has excellent cycle performance, and still has the specific discharge capacity of 161mAh/g after 100 cycles of 0.5C cycle.
Figure GDA0003152906160000084
Example 8
In a glove box, random copolymer P8
Figure GDA0003152906160000091
(n = m = 100) was dissolved in chloroform (30 wt%), coated on a positive electrode, and left to dry. The battery is assembled and the corresponding battery performance is tested, as shown in fig. 8, the battery has excellent cycle performance (the charge cut-off voltage is 1.8-2.8V) at room temperature, and still has the specific discharge capacity of 900mAh/g after 100 cycles of 0.1C cycle.
Figure GDA0003152906160000092
Example 9
In a glove box, random polymer P9
Figure GDA0003152906160000093
(N = m = 200) after dissolving N, N-dimethylacetamide (35 wt%), coating on the positive electrode, and standing to dry. The batteries were assembled and tested for their respective battery performances, as shown in fig. 9, and the batteries had excellent cycle performance (charge cutoff)The stopping voltage is 1.8-2.8V), and the discharging specific capacity of 780mAh/g can still be obtained after the battery is cycled for 100 circles at room temperature of 0.1C.
Figure GDA0003152906160000094
Figure GDA0003152906160000101
Example 10
In the glove box, polymer P10 was put in
Figure GDA0003152906160000102
(n = 90) after dimethyl sulfoxide (25 wt%) was dissolved, the solution was coated on a positive electrode, and left to dry. The battery is assembled and the corresponding battery performance is tested, as shown in fig. 7, the battery has excellent cycle performance (the charge cut-off voltage is 3.0-4.8V), the battery still has the discharge specific capacity of 120mAh/g after being cycled for 200 circles at room temperature at 0.5 ℃, and the capacity retention rate is 75%.
Figure GDA0003152906160000103
Example 11
In the glove box, polymer P11 was put in
Figure GDA0003152906160000104
(n =70,m = 10) and LiPF 6 (mass ratio =15 = 65) was mixed and dissolved in N, N-dimethylformamide, and then an electrolyte composite separator was prepared using glass fiber as a support material, which was applied to a lithium metal/lithium-rich manganese-based battery, as can be seen from fig. 11, the oxygen production at 0.5C for the first cycle of the battery was significantly reduced compared to a commercial liquid electrolyte.
Figure GDA0003152906160000105
Figure GDA0003152906160000111
Example 12
In the glove box, polymer P12 was put in
Figure GDA0003152906160000112
(n = 30) was dissolved in chloroform (35 wt%), applied as a binder to a lithium metal/ternary material battery (in the positive electrode content), and tested for gassing using in situ electrochemical mass spectrometry. As can be seen in fig. 12, the first cycle carbon dioxide production of the cell at 1C is significantly reduced over the commercial electrolyte.
Figure GDA0003152906160000113
Example 13
In the glove box, polymer P13 was put in
Figure GDA0003152906160000114
(n = 10) after dimethyl sulfoxide (25 wt%) was dissolved, the solution was coated on a positive electrode, and left to dry. The graphite/nickel lithium manganate battery of the battery is assembled, circulated at room temperature of 1 ℃, and the gas production of the first-circle battery is measured by using an in-situ electrochemical mass spectrum. As shown in FIG. 13, the yield of carbon monoxide was only 1.8g mol -1 Far below the carbon monoxide yield of commercial electrolytes.
Figure GDA0003152906160000115
Figure GDA0003152906160000121
Example 14
Random copolymer P14
Figure GDA0003152906160000122
(n =20,m = 100) as a bondAnd (3) preparing a lithium nickel manganese oxide positive electrode by using the agent (0.001%). The capacity retention rate of the assembled graphite/nickel lithium manganate battery after 300 cycles at room temperature of 2 ℃ is 80%.
Figure GDA0003152906160000123
Example 15
Subjecting the block copolymer P15
Figure GDA0003152906160000124
(n =5,m = 60) as a binder (20%), a lithium nickel cobalt manganese oxide (NCM 532) positive electrode was prepared. The capacity retention of the assembled battery was 53% after cycling at 60 degrees 2C for 200 cycles.
Figure GDA0003152906160000125
Figure GDA0003152906160000131
Example 16
Copolymer P16
Figure GDA0003152906160000132
(n =2000, m = 10) as a binder (10%), a lithium nickel cobalt manganese oxide (NCM 111) positive electrode was prepared. The capacity retention of the assembled battery was 90% after 100 cycles at 60 degrees 1C.
Figure GDA0003152906160000133
The method for testing the performance of the battery comprises the following steps:
(1) Preparation of positive plate
A, polyvinylidene fluoride (PVDF) is dissolved in N-methyl pyrrolidone, and the concentration is 0.1mol/L.
B, mixing a binder, a positive electrode active material and conductive carbon black in a ratio of 10:80:10, and grinding for at least 1 hour.
And C, uniformly scraping the slurry obtained in the previous step on an aluminum foil with the thickness of 100-120 microns, drying in a 60 ℃ drying oven, drying in a 120 ℃ vacuum drying oven, rolling, punching, weighing, continuously drying in the 120 ℃ vacuum drying oven, and placing in a glove box for later use.
(2) Preparation of negative plate
A PVDF was dissolved in N-methylpyrrolidone at a concentration of 0.1mol/L.
B, mixing PVDF, a negative electrode active material and conductive carbon black in a ratio of 10:80:10, and grinding for at least 1 hour.
And C, uniformly scraping the slurry obtained in the previous step on a copper foil with the thickness of 100-120 microns, drying in a 60 ℃ drying oven, drying in a 120 ℃ vacuum drying oven, rolling, punching, weighing, continuously drying in the 120 ℃ vacuum drying oven, and placing in a glove box for later use.
(3) Battery assembly
And placing the corresponding half cell or cell structure in a cell shell, and sealing to obtain the cell.
(4) Battery electrical performance testing
And testing the long cycle performance and the rate capability of the secondary lithium battery by using a LAND battery charge-discharge instrument.
The above examples are merely illustrative for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This is not exhaustive of all embodiments. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.

Claims (12)

1. Use of a polymer comprising a hindered amine structure in a secondary lithium battery, wherein: the polymer has a structure shown in a general formula (1):
Figure FDA0003908049150000011
wherein m is 0-2000 and n is 1-2000; a. The 1 、A 2 Each independently selected from H, COOH, CN, CONH 2 An alkoxycarbonyl group not more than eighteen carbon atoms, a perfluoroalkoxycarbonyl group not more than eighteen carbon atoms, an alkylaminoacyl group not more than eighteen carbon atoms, an alkyl group not more than eighteen carbon atoms, an alkoxy group not more than eighteen carbon atoms, an aryl group not more than eighteen carbon atoms,
Figure FDA0003908049150000012
the value of a is 1 to 250,
Figure FDA0003908049150000013
the value of b is 1 to 250,
Figure FDA0003908049150000014
c takes a value of 1 to 250;
Figure FDA0003908049150000015
B 1 is taken from NH, O, OCH 2 ；E - Is taken from PF 6 - ，BF 4 - ，TFSI - ，FSI - ，CH 3 OSO 3 - ，
Figure FDA0003908049150000016
Figure FDA0003908049150000017
B 2 Taken from NH, O, OCH 2 ，
Figure FDA0003908049150000018
v is 1-4; b is selected from O, OCH 2 (ii) a The value of W is 0-4; x is selected from H, oxygen free radical, alkoxy under octadecyl, alkyl under octadecyl, acyl under octadecyl; y is selected from H, methyl, methoxy, CN, F; z is selected from H, methyl, trifluoromethyl, chloromethyl, cyanomethyl;
the lithium battery comprises a negative electrode, a positive electrode, a diaphragm arranged between the negative electrode and the positive electrode and a non-aqueous electrolyte; the positive electrode comprises a positive active material, a binder, a conductive carbon material and a current collector; the polymer is coated on the surface of the positive electrode of the lithium battery;
the positive active material is one or more of lithium cobaltate, lithium manganese iron phosphate, lithium manganate, lithium nickel manganese oxide, lithium-rich manganese base, ternary material, lithium ion fluorophosphate and lithium manganese oxide;
the positive electrode having a surface coated with a polymer is prepared by the following method: dissolving a polymer in a solvent to form a uniform solution, spin-coating the solution containing the polymer on the surface of the positive electrode, and then drying the solution in a vacuum drying oven at 80 ℃ to obtain the positive electrode containing the polymer coating, wherein the thickness of the coating is 0.001-10 mu m.
2. The use of a polymer containing a hindered amine structure in a secondary lithium battery as claimed in claim 1, wherein: the polymer is selected from:
Figure FDA0003908049150000021
n＝80、
Figure FDA0003908049150000022
n＝40、
Figure FDA0003908049150000023
n＝5、
Figure FDA0003908049150000024
n＝3,m＝3、
Figure FDA0003908049150000031
n＝10、
Figure FDA0003908049150000032
n＝m＝100、
Figure FDA0003908049150000033
n＝m＝200、
Figure FDA0003908049150000034
n＝90、
Figure FDA0003908049150000035
n＝10。
3. the use of a polymer containing a hindered amine structure in a secondary lithium battery as claimed in claim 1, wherein: the active material of the negative electrode is one or more of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, carbon-silicon composite material, carbon-germanium composite material, carbon-tin composite material, antimony oxide, antimony-carbon composite material, tin-antimony composite material, lithium-titanium oxide and lithium metal nitride;
the binder of the positive electrode contains one or more polymers of claim 1, wherein the polymers account for 0.001-20% of the positive electrode material;
the diaphragm material is one of a cellulose non-woven film, a alginate fiber non-woven film, an aramid fiber non-woven film, a polyarylsulfone amide non-woven film, a polypropylene non-woven film, glass fiber, a polyethylene terephthalate film and a polyimide non-woven film;
the non-aqueous electrolyte comprises lithium salt, organic matrix and inorganic lithium ion conductor.
4. Use of a polymer comprising a hindered amine structure according to claim 3 in a secondary lithium battery, wherein: the lithium salt is lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoro (CF) 3 SO 3 One or more of Li), lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) and lithium bis (fluoro) sulfonyl imide (LiFSI);
the organic matrix is selected from the following group: the material comprises a polymer containing a hindered amine structure, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, diethyl carbonate, succinonitrile, ethanedinitrile, fluoroethylene carbonate, tetraethylene glycol dimethyl ether, sulfolane, polyethylene carbonate, polyacrylonitrile, polymethacrylate, polyethylene carbonate and polypropylene carbonate;
the inorganic lithium ion conductor is Li 3a La (2/3)-a TiO 3 ,0.04<a<0.14、Li 3+a X a Y 1-a O 4 ,X＝Si、Sc、Ge、Ti；Y＝P、As、V、Cr，0<a<1、LiZr 2 (PO 4 ) 3 、Li 7 La 3 Zr 2 O 12 、Li 1+a Al a Ti 2-a (PO 4 ) 3 ,0<a<2、Li 1+ a Al a Ge 2-a (PO 4 ) 3 ,0<a<2、Li 3 OCl、Li 3 OCl 0.5 Br 0.5 、Li 10 GeP 2 S 12 、Li 14 Zn(GeO 4 ) 4 、Li 5 La 3 M 2 O 12 ,M＝Ta、Nb、Li 5.5 La 3 Nb 1.75 In 0.25 O 12 、Li 3 N-LiX,X＝Cl、Br、I、Li 9-na M a N 2 Cl 3 ,M＝Na、K、Rb、Cs、Mg、Al，0<a<9，0<n<4、3Li 3 N-MI,X＝Li、Na、K、LiPON、Li 2 S-M a S b ,M＝Al、Si、P，0<a<3，0<b<6、Li 6 PS 5 X, X = F, cl, br, I.
5. The use of a polymer comprising a hindered amine structure in a secondary lithium battery as claimed in claim 1, wherein: the solvent for dissolving the polymer is one or more of dichloromethane, chloroform, 1,4-dioxane, glycol dimethyl ether, acetone, acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, diethyl sulfite, tetrahydrofuran, 1,2-dichloroethane, ethyl acetate, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the polymer accounts for 10-80% of the total weight of the solution.
6. The use according to claim 1, wherein the lithium ion fluorophosphate is selected from the group consisting of: lithium vanadium fluorophosphate, lithium iron fluorophosphate.
7. A lithium secondary battery comprising a negative electrode, a positive electrode, a separator interposed between the negative electrode and the positive electrode, and a nonaqueous electrolyte; wherein the content of the first and second substances,
the positive electrode comprises a positive active material, a binder, a conductive carbon material and a current collector;
the positive active material is one or more of lithium cobaltate, lithium manganese iron phosphate, lithium manganate, lithium nickel manganese, lithium-rich manganese base, ternary material, lithium ion fluorophosphate and lithium manganese oxide;
the surface of the lithium battery positive electrode is coated with a polymer with a hindered amine structure;
the positive electrode having a polymer coated surface was prepared by the following method: dissolving a polymer in a solvent to form a uniform solution, spin-coating the solution containing the polymer on the surface of a positive electrode, and then drying the solution in a vacuum drying oven at 80 ℃ to obtain the positive electrode containing a polymer coating, wherein the thickness of the coating is 0.001-10 mu m;
the polymer has a structure shown in a general formula (1):
Figure FDA0003908049150000041
Figure FDA0003908049150000051
wherein m is 0-2000 and n is 1-2000; a. The 1 、A 2 Independently of each other from H, COOH, CN, CONH 2 Alkoxycarbonyl of not more than eighteen carbon, perfluoroalkoxycarbonyl of not more than eighteen carbon, alkylaminoacyl of not more than eighteen carbon, alkyl of not more than eighteen carbon, decaAlkoxy of eight carbons or less, aryl of eighteen carbons or less,
Figure FDA0003908049150000052
the value of a is 1 to 250,
Figure FDA0003908049150000053
the value of b is 1 to 250,
Figure FDA0003908049150000054
c takes a value of 1 to 250;
Figure FDA0003908049150000055
B 1 is taken from NH, O, OCH 2 ；E - Is taken from PF 6 - ，BF 4 - ，TFSI - ，FSI - ，CH 3 OSO 3 - ，
Figure FDA0003908049150000056
Figure FDA0003908049150000057
B 2 Is taken from NH, O, OCH 2 ，
Figure FDA0003908049150000058
v is 1-4; b is selected from O, OCH 2 (ii) a The value of W is 0-4; x is selected from H, oxygen free radical, alkoxy under octadecyl, alkyl under octadecyl, acyl under octadecyl; y is selected from H, methyl, methoxy, CN, F; z is selected from H, methyl, trifluoromethyl, chloromethyl and cyanomethyl.
8. A lithium secondary battery as claimed in claim 7, characterized in that said polymer is selected from the group consisting of:
Figure FDA0003908049150000059
n＝80、
Figure FDA00039080491500000510
n＝40、
Figure FDA0003908049150000061
n＝5、
Figure FDA0003908049150000062
n＝3,m＝3、
Figure FDA0003908049150000063
n＝10、
Figure FDA0003908049150000064
n＝m＝100、
Figure FDA0003908049150000065
n＝m＝200、
Figure FDA0003908049150000066
n＝90、
Figure FDA0003908049150000067
n＝10。
9. the secondary lithium battery as claimed in claim 7, wherein the active material of the negative electrode is one or more of metallic lithium, metallic lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, carbon-silicon composite material, carbon-germanium composite material, carbon-tin composite material, antimony oxide, antimony-carbon composite material, tin-antimony composite material, lithium-titanium oxide, and lithium metal nitride;
the binder of the positive electrode contains one or more polymers of claim 1, wherein the polymers account for 0.001-20% of the positive electrode material;
the diaphragm material is one of a cellulose non-woven film, a alginate fiber non-woven film, an aramid fiber non-woven film, a polyarylsulfone amide non-woven film, a polypropylene non-woven film, glass fiber, a polyethylene terephthalate film and a polyimide non-woven film;
the non-aqueous electrolyte comprises lithium salt, organic matrix and inorganic lithium ion conductor.
10. The secondary lithium battery of claim 9 wherein said lithium salt is lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium trifluoro (CF) 3 SO 3 Li), lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) and lithium bis (fluoro) sulfonyl imide (LiFSI);
the organic matrix is selected from the following group: the material comprises a polymer containing a hindered amine structure, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, diethyl carbonate, succinonitrile, ethanedinitrile, fluoroethylene carbonate, tetraethylene glycol dimethyl ether, sulfolane, polyethylene carbonate, polyacrylonitrile, polymethacrylate, polyethylene carbonate and polypropylene carbonate;
the inorganic lithium ion conductor is Li 3a La (2/3)-a TiO 3 ,0.04<a<0.14、Li 3+a X a Y 1-a O 4 ,X＝Si、Sc、Ge、Ti；Y＝P、As、V、Cr，0<a<1、LiZr 2 (PO 4 ) 3 、Li 7 La 3 Zr 2 O 12 、Li 1+a Al a Ti 2-a (PO 4 ) 3 ,0<a<2、Li 1+ a Al a Ge 2-a (PO 4 ) 3 ,0<a<2、Li 3 OCl、Li 3 OCl 0.5 Br 0.5 、Li 10 GeP 2 S 12 、Li 14 Zn(GeO 4 ) 4 、Li 5 La 3 M 2 O 12 ,M＝Ta、Nb、Li 5.5 La 3 Nb 1.75 In 0.25 O 12 、Li 3 N-LiX,X＝Cl、Br、I、Li 9-na M a N 2 Cl 3 ,M＝Na、K、Rb、Cs、Mg、Al，0<a<9，0<n<4、3Li 3 N-MI,X＝Li、Na、K、LiPON、Li 2 S-M a S b ,M＝Al、Si、P，0<a<3，0<b<6、Li 6 PS 5 X, X = F, cl, br and I.
11. The lithium secondary battery of claim 7 wherein the solvent to dissolve the polymer is one or more of dichloromethane, chloroform, 1,4-dioxane, ethylene glycol dimethyl ether, acetone, acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, diethyl sulfite, tetrahydrofuran, 1,2-dichloroethane, ethyl acetate, N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide, and wherein the polymer comprises 10% to 80% of the total weight of the solution.
12. A lithium secondary battery as claimed in claim 7, characterized in that the lithium ion fluorophosphate is selected from the group consisting of: lithium vanadium fluorophosphate, lithium iron fluorophosphate.
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