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Vinylidene fluoride copolymer suitable for binder and its preparation method and application

A vinylidene fluoride-like copolymer technology, which is applied in the field of vinylidene fluoride-like copolymers and its preparation, can solve the problem of high raw material cost and limitations of PVDF-based binders, and PVDF-based binders cannot be used with strong alkalinity environmental issues

Active Publication Date: 2020-10-23
BYD CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] (1) The raw material cost of PVDF binder is high;
[0004] (2) PVDF binders cannot be used in strong alkaline environments
[0005] (3) PVDF binders can only be dissolved in limited types of organic solvents such as NMP, DMF, and DMSO, which limits their application in specific experimental processes and the improvement of corresponding processes

Method used

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  • Vinylidene fluoride copolymer suitable for binder and its preparation method and application
  • Vinylidene fluoride copolymer suitable for binder and its preparation method and application

Examples

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preparation example Construction

[0046] The second aspect of the present invention provides a method for preparing a vinylidene fluoride copolymer, the method comprising: in the presence of a free radical initiator, in an organic solvent, the monomer represented by formula (1-a), the formula The monomer shown in (2-a) and the monomer shown in formula (3-a) carry out copolymerization reaction, wherein,

[0047] Formula (1-a) Formula (2-a) CF 2 =CH 2 , formula (3-a)

[0048] Wherein, Z is each independently selected from a single bond, -(C m h 2m )-,-(C m f 2m )-, -(CH 2 CH 2 O) m -, -(OCH 2 CH 2 ) m -, -(CO)-O- or -O-(CO)-, k is each independently an integer of 1-5, and m is each independently an integer of 1-20;

[0049] R f for-C h f 2h+1 , h is an integer of 0-10; R f1 , R f2 and R f3 each independently -C i h 2i+1 or -C i f 2i+1 , i is an integer of 0-10;

[0050] Cationic Y + for H + , Li + 、Na + 、K + , Rb + 、Cs + , Mg 2+ , Ca 2+ 、Sr 2+ 、Ba 2+ 、Al 3+ , the cation sho...

preparation example 1

[0092]

[0093] Prepare the monomer according to the above reaction formula, specifically:

[0094] (1) Take 1.9164g (10mmol) of p-chlorobenzenesulfonamide, 2.3794g (20mmol) of thionyl chloride, and 1.3982g (12mmol) of chlorosulfonic acid at 100°C for 12h to obtain compound 1a (2.6113g, yield 90%); 1 H NMR (400MHz, CDCl 3 , ppm), δ=7.87(d, 2×1H), 7.55(d, 2×1H), 2.0(s, 1H).

[0095] (2) Take 2.9014g (10mmol) of compound 1a and 2.1451g (12mmol) of SbF 3 Reacted at 60°C for 12h to obtain compound 1b (2.4632g, yield 90%); 1 H NMR (400MHz, CDCl 3 , ppm), δ=7.87(d, 2×1H), 7.55(d, 2×1H), 2.0(s, 1H).

[0096] (3) Take 2.7369g (10mmol) of compound 1b and 0.7389g (10mmol) of Li 2 CO 3 Reacted at 25°C for 2h to obtain compound 1c (2.7962g, yield 100%); 1 H NMR (400MHz, CDCl 3 , ppm), δ=7.87(d, 2×1H), 7.55(d, 2×1H), 2.0(s, 1H).

[0097] (4) While cooling with an ice-salt bath, 2.7962 g (10 mmol) of compound 1c was taken, and 10 mL of a tetrahydrofuran solution of 1.6015 g (25...

Embodiment 1

[0100] This example is used to illustrate the vinylidene fluoride copolymer of the present invention and its preparation method.

[0101] Take 6.144g (20mmol) of the compound represented by the formula (1-a-1), 0.1mmol of di-tert-butyl peroxide and 20mL of acetonitrile and mix them uniformly. While heating and stirring at 70° C., a mixed gas (about 20 mmol) of vinylidene fluoride and hexafluoropropylene with a molar ratio of 99:1 was introduced. After the gas feeding process is completed, continue to react for 24h; filter the obtained product, dissolve the solid with 10mL of ethanol, then add 50mL of ether for recrystallization, repeat the recrystallization three times, and then vacuum dry the obtained solid to obtain a white powder The vinylidene fluoride copolymer P1;

[0102] Wherein, the weight average molecular weight of the vinylidene fluoride copolymer is 300,000g / mol, the molecular weight distribution index is 1.3, the structural unit shown in formula (1-1), the struc...

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Abstract

The invention relates to the field of lithium batteries, in particular to vinylidene fluoride-based copolymers suitable for a binding agent as well as a preparation method and application of the copolymers. The vinylidene fluoride-based copolymers contain a structural unit represented by a formula (1) shown in the description, a structural unit represented by a formula (2) shown in the description, and a structural unit represented by a formula (3) shown in the description. The novel vinylidene fluoride-based copolymers provided by the invention can be well dissolved into large polar and non-polar solvents; at the same time, the copolymers have better tolerance to a strong alkali environment; and the copolymers can reduce influence of the binding agent in a small pole piece on ion migration; therefore, when the copolymers are used as the binding agent in a lithium battery, the obtained lithium battery can have higher specific capacity and cycle performance.

Description

technical field [0001] The invention relates to the field of lithium batteries, in particular to a vinylidene fluoride copolymer suitable for a binder, a preparation method and application thereof. Background technique [0002] PVDF-based binders are conventional binders in the field of lithium-ion battery preparation, usually including pure polyvinylidene fluoride, modified polymers of polyvinylidene fluoride, or copolymerized by vinylidene fluoride and hexafluoropropylene of polymers. The main unit in the polymer chain structure of these binders is vinylidene fluoride unit. However, the existing PVDF binders have the following defects: [0003] (1) The raw material cost of PVDF binder is high; [0004] (2) PVDF binders cannot be used in strong alkaline environments. It is easy to defluorinate in the solution with pH>10, and it will lead to the failure of the binder at the same time. This phenomenon will be reflected in the preparation of the ternary cathode materia...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F214/22C08F214/28C08F214/18H01M4/62H01M10/052
CPCY02E60/10
Inventor 宋威郭姿珠
Owner BYD CO LTD
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