CN103804599B - Polymer, the electrode for lithium battery containing it and the lithium battery containing the electrode - Google Patents

Abstract

Polymer including the first repetitive unit indicated by formula 1, the polymer composition for lithium battery including the polymer, the electrode for lithium battery including the polymer composition, with the lithium battery including the electrode, wherein, in formula 1, what R, R ', A, A ', Y and Y ' were defined as in the description.Formula 1

Description

Polymer, the electrode for lithium battery containing it and the lithium battery containing the electrode

Cross reference to related applications

This application claims the priority for the South Korea patent application No.10-2012-0129097 that on November 14th, 2012 submits With equity and the ownership equity being generated by it, content is by reference to being fully incorporated herein.

Technical field

Present inventive concept is related to polymer, including the polymer for the electrode of lithium battery and including the electrode Lithium battery.

Background technique

Lithium battery has high voltage and high energy density, and therefore can be used in a variety of applications.For example, hybrid power Electric vehicle (" HEV "), plug-in hybrid-power electric vehicle (" PHEV ") etc. should be it is can running at high temperature, can will be a large amount of Electricity is charged and discharged, has long-term availability, and the lithium electricity for the discharge capacity and better life characteristic for therefore needing to have high Pond.

In order to improve capacity and the service life of lithium battery, other than novel anode and negative material, has been carried out many and grind Study carefully to develop the novel binders for being used for lithium battery.

The example of most generally used binder is Kynoar (" PVDF "), butadiene-styrene rubber (" SBR ") and carboxymethyl Sodium cellulosate (" Na-CMC ").

The granularity of negative electrode active material is smaller and specific surface area is bigger, connecing between negative electrode active material and electrolyte solution Contacting surface product becomes bigger, so that during the initial insertion of lithium ion can be more likely to that electrolyte solution and negative electrode active material occurs Between side reaction.This can lead to increased initial irreversible capacitance, and therefore lead to the low starting efficiency of lithium battery.Cause This, however it remains is for the needs of the lithium battery with improved starting efficiency.

Summary of the invention

New polymers is provided.

The electrode for lithium battery including the polymer is provided.

Lithium battery including the electrode is provided.

In addition aspect will be partly articulated in the following description, and partly will be apparent from the description, or can be led to The practice for crossing provided embodiment is learned.

The one aspect conceived according to the present invention, polymer include the first repetitive unit indicated by following formula 1:

Formula 1

Wherein, in formula 1,

R and R ' is each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 Alkoxy, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 Aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C2- C30 heteroaryl, substituted or unsubstituted C2-C30 heteroaryloxy, substituted or unsubstituted C3-C30 heteroarylalkyl, replace or not Substituted C4-C30 carbon ring group, substituted or unsubstituted C5-C30 carbocylic radical alkyl, substituted or unsubstituted C2-C30 heterocycle Group or substituted or unsubstituted C3-C30 heterocyclylalkyl group；

A and A ' is each independently-C (=O) O- ,-C (=O)-,-OS (=O)₂O-、(-OS(=O)O-)、-S(=O)₂O-、-S (=O)O-、-OP(=O)O₂Or-P (=O) O₂-；With

Y and Y' is each independently hydrogen atom, alkali metal, ammonium or-NH₂, condition is that Y and Y' are not simultaneously hydrogen atom Or NH₂。

The another aspect conceived according to the present invention, the polymer as reaction product below is provided:

(i) alkali of alkali metal containing or ammonium, and

It (ii) include by the following Expression 4 c or formula 4d the first repetitive unit indicated and selected from divalent aliphatic organic group weight The polymer A of second repetitive unit of multiple unit and divalent alicyclic organic group repetitive unit:

Formula 4c

Wherein, in formula 4c,

R₇And R₈It is each independently hydrogen atom or C1-C10 alkyl；

Formula 4d

Wherein, in formula 4d,

R₇And R₈It is each independently hydrogen atom or C1-C10 alkyl.

The molar fraction of first repetitive unit be about 0.01- about 0.99 and second repetitive unit mole point Number is about 0.01- about 0.99.

The another aspect conceived according to the present invention, include: for the electrode of lithium battery

Polymer including the first repetitive unit indicated by equation 1 above；With

Electrode active material.

The another aspect conceived according to the present invention, lithium battery includes above-mentioned electrode.

Detailed description of the invention

By being described below for the embodiment that is considered in conjunction with the accompanying, these and/or other aspects will be apparent and more hold It is readily understood, in which:

Fig. 1 is the decomposition perspective view according to the lithium battery of the embodiment of present inventive concept；

Fig. 2-4 is the polymer illustrated according to preparation embodiment 1-6 preparation¹The intensity of H- nuclear magnetic resonance (" NMR ") spectrum The figure of (arbitrary unit, a.u.) to chemical shift (parts per million, ppm)；

Fig. 5-6 is the polymer illustrated according to preparation embodiment 1-6 preparation¹The result of H- nuclear magnetic resonance (" NMR ") spectrum Chemical shift (parts per million, ppm) to the figure of lithium degree of substitution.

Specific embodiment

Now by new polymers, respectively including the polymer the electrode and lithium battery for being used for lithium battery implementation Mode describes in detail, and the example is illustrated in attached drawing, wherein identical appended drawing reference refers to identical element always.At this On point, present embodiment can have different forms and should not be construed as limited by description set forth herein.Therefore, only lead to below It crosses and describes embodiment with reference to the accompanying drawings, to explain the aspect of this description.Term "and/or" as used in this article includes related institute One or more any and all combinations of list of items.Statement such as " ... at least one (kind) " is when before element list Or when later, modifies entire element list and do not modify the independent element of the list.

It will be understood that when an element such as layer, film, region or substrate are referred to as " " other element "upper", it can Directly on the other element, or intermediary element also may be present.On the contrary, when an element is referred to as " directly existing " in addition Element "upper" when, then be not present intermediary element.

It will be understood that although term first, second, third, etc. can herein be used to describe various elements, component, region, Layer and/or part, but these elements, component, regions, layers, and/or portions should not be limited by these terms.These terms are only used to An element, component, region, layer or part is set to be different from another element, component, region, layer or part.Therefore, without departing substantially from In the case where the introduction of present embodiment, first element discussed below, component, region, layer or part can be described as second element, Component, region, layer or part.

Term used herein is just for the sake of description specific embodiment and is not intended to restrictive.As herein The singular " a kind of (a) " used and " (being somebody's turn to do) " are also intended to include plural form, unless in addition context is clearly said It is bright.It will be further understood that, term " includes " and/or "comprising" indicate that there are the features, area where used in this disclosure Domain, entirety, step, operation, element and/or component, but do not preclude the presence or addition of one or more other features, region, Entirety, step, operation, element, component and/or its set.

Unless otherwise defined, the meaning of all terms (including technical and scientific term) used herein and this total hair The normally understood meaning of bright design those of ordinary skill in the art is identical.It will be further understood that, term, such as in commonly used word Those, should be interpreted its meaning and their meanings one in related fields and the background of present disclosure defined in allusion quotation The explanation for causing, and idealization or excessively forms choice being carried out to the term, unless clearly so fixed herein Justice.

The embodiment conceived according to the present invention, provides new polymers comprising the first repetition indicated by following formula 1 is single Member:

Formula 1

In equation 1 above,

R and R ' is each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 Alkoxy, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 Aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C2- C30 heteroaryl, substituted or unsubstituted C2-C30 heteroaryloxy, substituted or unsubstituted C3-C30 heteroarylalkyl, replace or not Substituted C4-C30 carbon ring group, substituted or unsubstituted C5-C30 carbocylic radical alkyl, substituted or unsubstituted C2-C30 heterocycle Group or substituted or unsubstituted C3-C30 heterocyclylalkyl group；

A and A ' is each independently-C (=O) O- ,-C (=O)-,-OS (=O)₂O-、(-OS(=O)O-)、-S(=O)₂O-、-S (=O)O-、-OP(=O)O₂Or-P (=O) O₂-；With

Y and Y' is each independently hydrogen atom, alkali metal, ammonium or-NH₂, condition is that Y and Y' is not simultaneously hydrogen original Son or-NH₂。

In formula 1, A and A ' are bivalent group and can be each independently carboxylate group as described above (- C (=O) O-), sulfate groups (- OS (=O)₂O-), inferior sulfate radical group (- OS (=O) O-), sulfonate group (- S (=O)₂O-), sub- sulphur Sulfonate groups (- S (=O) O-), phosphate groups (- OP (=O) O₂), phosphonate groups (- P (=O) O₂) or carbonyl.

When A and A' are each independently phosphate groups or phosphonate groups ,-A-Y be can be selected from by following 1 table of structural formula The functional group shown, and-A'-Y' can be selected from the functional group indicated by following structural formula 2:

Structural formula 1

Structural formula 2

Wherein in structural formula 1 and 2,

Y and Y' is each independently hydrogen atom, alkali metal or ammonium, and condition is that Y and Y' are not simultaneously hydrogen atom.

First repetitive unit of equation 1 above can be indicated by following formula 2 or 2a:

2 formula 2a of formula

In formula 2 and 2a,

R₁And R₂It is each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 Alkoxy, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 Aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C2- C30 heteroaryl, substituted or unsubstituted C2-C30 heteroaryloxy, substituted or unsubstituted C3-C30 heteroarylalkyl, replace or not Substituted C4-C30 carbon ring group, substituted or unsubstituted C5-C30 carbocylic radical alkyl, substituted or unsubstituted C2-C30 heterocycle Group or substituted or unsubstituted C3-C30 heterocyclylalkyl group；With

Y₁And Y₂It is each independently hydrogen atom, alkali metal, ammonium or-NH₂, condition is Y₁And Y₂It is not simultaneously hydrogen original Son or-NH₂。

The example of the ammonium is unsubstituted ammonium-NH₄Or the ammonium replaced by one to three substituent group, the substitution Base includes C1-C30 alkyl, C6-C30 aryl, C7-C30 aralkyl, C2-C30 heteroaryl, C4-C30 carbon ring group and C2-C30 At least one of heterocyclic group.

The polymer can further comprise the second repetitive unit.Second repetitive unit may include that divalent aliphatic is organic Group repetitive unit or divalent alicyclic organic group repetitive unit.

The divalent aliphatic organic group repetitive unit can refer to for example substituted or unsubstituted C1-C30 alkylidene or take The repetitive unit of generation or unsubstituted C2-C30 alkynylene, and in some embodiments, can refer to such as C1-C15 alkylidene or The repetitive unit of C2-C15 alkynylene.

The divalent alicyclic organic group repetitive unit can refer to such as C3-C30 cycloalkylidene or the Asia C3-C30 cycloalkynyl radical Repetitive unit, and in some embodiments, can refer to C3-C15 cycloalkylidene or the Asia C3-C15 cycloalkynyl radical.

Second repetitive unit can be the second repetitive unit indicated by following formula 3:

Formula 3

In formula 3, R₃-R₆It is each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C7-C30 aralkyl, replace or do not take The C2-C30 heteroaryl in generation, substituted or unsubstituted C3-C30 heteroarylalkyl, takes substituted or unsubstituted C2-C30 heteroaryloxy Generation or unsubstituted C4-C30 carbon ring group, substituted or unsubstituted C5-C30 carbocylic radical alkyl, substituted or unsubstituted C2- C30 heterocyclic group or substituted or unsubstituted C2-C30 heterocyclylalkyl group；Or

R₃With R₄Or R₅With R₆It can be independently connected together to form ring, wherein the ring can be C6-C10 cycloalkanes Base, C3-C10 heteroaryl, condensed C3-C10 heteroaryl, C3-C10 heterocyclic group or condensed C3-C10 heterocyclic group.

In some embodiments, the polymer can further comprise the third repeating list indicated by following formula 4a or 4b Member:

Formula 4a

Formula 4b

In formula 4a and 4b, R1 and R2 be each independently hydrogen atom, substituted or unsubstituted C1-C30 alkyl, replace or Unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, replace or Unsubstituted C6-C30 aryl, substituted or unsubstituted C7-C30 aralkyl, replaces substituted or unsubstituted C6-C30 aryloxy group Or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C2-C30 heteroaryloxy, substituted or unsubstituted C3-C30 heteroaryl It is alkyl, substituted or unsubstituted C4-C30 carbon ring group, substituted or unsubstituted C5-C30 carbocylic radical alkyl, substituted or unsubstituted C2-C30 heterocyclic group or substituted or unsubstituted C3-C30 heterocyclylalkyl group.

The polymer can be include the first repetitive unit indicated by following formula 4 or 4g, second repeated by following formula 5 indicates The polymer of unit and the third repeating unit by following formula 4a or 4b expression.

4 formula 4g of formula

In formula 4 and 4g, R₇And R₈Hydrogen atom or C1-C10 alkyl can be each independently；

Y₃And Y₄It is each independently hydrogen atom, Li, Na, K or NH₄, condition is Y₃And Y₄It is not simultaneously hydrogen atom；With

Formula 5

In formula 5,

R₉-R₁₂It is each independently hydrogen atom or C1-C10 alkyl.

Formula 4_a

Formula 4b

In formula 4a and formula 4b, R₁And R₂Hydrogen atom can be each independently, substituted or unsubstituted C1-C30 alkyl, taken Generation or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 alkynyl, take substituted or unsubstituted C2-C30 alkenyl Generation or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy group, substituted or unsubstituted C7-C30 aralkyl, Substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C2-C30 heteroaryloxy, substituted or unsubstituted C3-C30 Heteroarylalkyl, substituted or unsubstituted C4-C30 carbon ring group, substituted or unsubstituted C5-C30 carbocylic radical alkyl, replace or not Substituted C2-C30 heterocyclic group or substituted or unsubstituted C3-C30 heterocyclylalkyl group.

The sum of the molar fraction of first repetitive unit and the molar fraction of second repetitive unit can be 1.For example, The molar fraction of first repetitive unit and second repetitive unit can be respectively about 0.01-0.99.

The sum of molar fraction and the molar fraction of the third repeating unit of second repetitive unit can be 1.For example, The molar fraction of second repetitive unit and the third repeating unit can be respectively about 0.01-0.99.

The molar fraction of first repetitive unit, the molar fraction of second repetitive unit and the third repeating list The sum of molar fraction of member can be 1.For example, the molar fraction of first repetitive unit, second repetitive unit and described The molar fraction of the third repeating unit can respectively be about 0.01-0.99.

In some embodiments, described includes the first repetitive unit indicated by formula 4 or 4g, indicated by formula 5 second Repetitive unit and the degree of polymerization that can have about 100- about 50,000 by the polymer of formula 4a or the 4b the third repeating unit indicated.

Another embodiment conceived according to the present invention, provides the polymer as reaction product below:

(i) alkali of alkali metal containing or ammonium and

It (ii) include being repeated by following formula 4c or formula 4d the first repetitive unit indicated and selected from divalent aliphatic organic group The polymer A of second repetitive unit of unit and divalent alicyclic organic group repetitive unit:

Formula 4c

In formula 4c,

R₇And R₈It is each independently hydrogen atom or C1-C10 alkyl；

Formula 4d

In formula 4d,

R₇And R₈It is each independently hydrogen atom or C1-C10 alkyl；With

The molar fraction of first repetitive unit is the molar fraction of about 0.01- about 0.99 and second repetitive unit It is about 0.01- about 0.99.

In some embodiments, second repetitive unit of the polymer A can be for by second repetition of the expression of following formula 5 Unit:

Formula 5

In formula 5,

R₉-R₁₂It is each independently hydrogen atom or C1-C10 alkyl.

In some embodiments, as i) alkali metal containing or the alkali and ii of ammonium) include formula 4c or 4d first repeat Unit and selected from divalent aliphatic organic group repetitive unit and divalent alicyclic organic group repetitive unit second repeat it is single The polymer of the reaction product of the polymer A of member can have the degree of polymerization of about 100- about 50,000.

It will include by formula 4c or formula 4d the first repetitive unit indicated and choosing that the reaction product, which can be achieved in that, From the polymer of divalent aliphatic organic group repetitive unit and the second repetitive unit of divalent alicyclic organic group repetitive unit, The alkali and water of alkali metal containing or ammonium are mixed to obtain mixture；And at about 20 DEG C-about 100 DEG C and in embodiments 50 The mixture is heat-treated at a temperature of DEG C -80 DEG C.

The alkali of the alkali metal containing or ammonium can be any alkali for including alkali metal or ammonium.As the alkali metal containing or At least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonium hydroxide can be used in the non-limiting example of the alkali of ammonium Kind.The polymer of the second repetitive unit based on the first repetitive unit and formula 5 that described in 1 mole include formula 4c or 4d, it is described The amount of the alkali of alkali metal containing or ammonium can be 0.2 mole -1.0 moles, and in embodiments, about 0.4-0.8 moles.When described The amount of the alkali of alkali metal containing or ammonium within the above range when, can get have the scheduled substitution by the alkali metal or ammonium The polymer of degree.

0.2- about 1.0 can be about by the degree of substitution of alkali metal or ammonium in the polymer, and in some embodiments, About 0.4- about 1.0.The example of the alkali metal is lithium.The example of the ammonium is NH₄.The example of the alkali of the alkali metal containing is Lithium hydroxide.The example of the alkali containing ammonium is ammonium hydroxide.

In some embodiments, the second repetitive unit of first repetitive unit and formula 5 including formula 4c or 4d Polymer can have about 50,000- about 500,000 and the in embodiments weight average molecular weight of about 100,000- about 500,000. When the weight average molecular weight of the polymer is in aforementioned range, the viscosity of the composition comprising the polymer is suitably adapted for electricity The manufacture of pole.

In some embodiments, the second of the first repetitive unit including formula 4c or 4d prepared as described above and formula 5 The polymer of repetitive unit can be¹H nuclear magnetic resonance ("¹H-NMR ") in spectrum in 2.65 parts per million (" ppm ") -2.75ppm and At least one of the maleic anhydride and maleic acid in auto polymerization object chain is showed in the chemical shift range of 2.2ppm-2.4ppm Two proton peaks.

In the polymer¹In H-NMR spectrum, proton peak in the chemical shift range of 2.2ppm-2.4ppm with The peak integral ratio of proton peak in the chemical shift range of 2.65ppm-2.75ppm can be about 0.95- about 1.05.

In some embodiments, polymer composition can further comprise water.

In some embodiments, the polymer may include the first repetitive unit of following formula 6 or 6a, following formula 7 second Repetitive unit and the third repeating unit indicated by formula 4e or 4h:

6 formula 6a of formula

In formula 6, Y₅And Y₆It is each independently hydrogen atom, Li, Na, K, ammonium or-NH₂, condition is Y₅And Y₆It can not be same When be hydrogen atom or-NH₂。

Formula 7

Formula 4e formula 4h

In some embodiments, first repetitive unit including formula 6 or 6a, formula 7 the second repetitive unit and formula The polymer of the third repeating unit of 4e or 4h can have about 100- about 50,000 and in embodiments about 50 about 1,000-, 000 degree of polymerization.

Formula 6 or formula 6a in the polymer of either one or two of embodiment of above according to the present invention, in the polymer The molar fraction of the first repetitive unit and the sum of the molar fraction of the second repetitive unit of formula 7 can be 1.For example, described first The molar fraction of repetitive unit and the second repetitive unit can be respectively about 0.01-0.99.

In the polymer of either one or two of embodiment of above according to the present invention, the second repetitive unit of equation 7 above rubs The sum of molar fraction of the third repeating unit of that score and formula 4e or 4h can be 1.For example, second repetitive unit and described The molar fraction of the third repeating unit can be respectively about 0.01-0.99.

In some embodiments, first repetitive unit including formula 6 or 6a, formula 7 the second repetitive unit and formula The polymer of the third repeating unit of 4h can be for by the polymer of following formula 8 or 8z expression:

Formula 8

Formula 8z

In formula 8 and 8z, i) Y₇And Y₈It can be both lithium or ii) Y₇And Y₈One of can be lithium, and remaining can be former for hydrogen Son；

A can be the molar fraction of 0 or about 0.01- about 0.99, and b can be the molar fraction and a+b of 1 or about 0.01- about 0.99 =1；

M can be about the molar fraction of 0.01- about 0.99, and n can be about molar fraction and m+n=1 of 0.01- about 0.99.By The polymer that formula 8 or 8z are indicated can have the degree of polymerization of about 100- about 50000.

In some embodiments, pattern of rows and columns depending on the first repetitive unit and the second repetitive unit, by formula 8 or 8z The polymer of expression can be alternating polymer, atactic polymer or block polymer.

In embodiments, the polymer can have through inductively coupled plasma atomic emission spectrometry (ICP- AES) the lithium content of the about 15 weight % of about 2 weight %- measured.When the lithium content of the polymer is in aforementioned range, use The lithium battery of the polymer can be improved in terms of service life and starting efficiency.

In embodiments, the polymer can be prepared into polymer composition by adding water.Based on 100 parts by weight The amount of the polymer, the water in the polymer composition can be about about 5000 parts by weight of 400 parts by weight-.When the water Amount in the range when, the polymer can have good dissolubility and resulting polymer composition that can have to be suitable for Form the viscosity of electrode active material layer.

The granularity and surface area of electrode active material are an important factor for influencing battery behavior.The granularity of electrode active material Smaller and surface area is bigger, and the performance of battery becomes better, for example, power output, capacity under low temperature and high magnification and putting In terms of capacitance.However, the smaller particle size and large specific surface area of electrode active material can lead to electrode active material and electrolysis Increased contact area between matter solution, so that can be more likely to that electrolyte solution and electrode active occurs during the insertion of initial lithium Side reaction between property substance.This can lead to the increased initial irreversible capacitance of electrode active material, and therefore lead to lithium The low starting efficiency of battery, and thus need further improvement in this regard.

The high starting efficiency of lithium battery can lead to the higher actual capacity relative to design capacity, and therefore cause compared with High energy density.In this regard, in order to improve the starting efficiency of battery, need to design control with prevent electrode active material and Direct contact between electrolyte solution.

In some embodiments, the polymer in the polymer composition, which is used as, includes alkali metal such as lithium Or the water-soluble polymer of ammonium can be used as binder.The polymer as binder can cover the table of electrode active material Face, therefore effectively blocking electrode active contacts electrolyte solution.Therefore, with use conventional water-soluble binder phase Than the side reaction between electrode active material and electrolyte solution can occur in which may be less likely to, and the therefore initial effect of lithium battery Rate can improve.

In the polymer according to the polymer composition of embodiment of above, the oxygen that lithium ion is come from-C (=O) O- is former The coordination of son forms the conducting path of lithium ion, as illustrated by following formula:

In above formula, for convenience of description, the molar fraction of each repetitive unit is not described.The polymer can have about 100- about 50,000 and the in embodiments polymerization degree n of about 1,000- about 50,000.

Compared with when using Lithium polyacrylate as binder, the formation in lithium ion conduction path as described above can will Twice of lithium substitution reaction promotion or more.Therefore, when use the polymer composition as binders for electrodes formed electrode When active material layer, the electrode with improved ionic conductivity can get.

In addition, in the case where using the polymer composition as binders for electrodes, the polymer composition Polymer can form organosilicon prepolymer solid electrolyte interface (" pre-SEI ") film on the surface of electrode active material to cover electrode The defect of active material and the direct contact between blocking electrode active material and electrolyte solution, thus inhibit side reaction and because This improves the starting efficiency of the lithium battery.

In some embodiments, the polymer can be the polymer indicated by the following Expression 8 e, formula 8b, formula 9 or formula 9a.

Formula 8e

In formula 8e, i) Y₇And Y₈It can be both lithium and/or ii) Y₇And Y₈One of can be lithium, and remaining can be former for hydrogen Son；With a can be 0.2,0.3,0.4,0.5 or 0.8 molar fraction and a+b can be 1.

Formula 8b

Formula 9

In formula 9, a 0.1-0.9 and b are 0.1-0.9.

Formula 9a

The polymer indicated by formula 8e can also be indicated by following formula 8f.

Formula 8f

In formula 8f, a can be 0.2,0.3,0.4,0.5 or 0.8 molar fraction and a+b can be 1.

The embodiment conceived according to the present invention provides the polymer by the following Expression 10 or formula 10a expression.

Formula 10

In formula 10, a and b can be respectively 0.5 molar fraction.

Formula 10a

The polymer of equation 10 above or 10a can have the degree of polymerization of about 2,500- about 3,500.

In the polymer according to above embodiment, rub when the two kinds of repetitive units distinguished with round parentheses are having the same When your score, the molar fraction of the repetitive unit is omitted.

Hereinafter, the preparation that the embodiment conceived according to the present invention will be described in further detail is used for the polymerization of lithium battery The method of compositions.As example, description is prepared into polymer composition using by the polymer that equation 8 above indicates.

Firstly, by the alkali of the polymer indicated by following formula 9c or the polymer and alkali metal containing or ammonium that are indicated by formula 9d and Water is to obtain mixture:

Formula 9c

Formula 9d

In formula 9c and 9d, m and n can be respectively the molar fraction of about 0.01- about 0.99.

The polymer of formula 9c or 9d can have the degree of polymerization of about 100- about 50,000.

By the mixture about 20 DEG C-about 95 DEG C at a temperature of be heat-treated to obtain the polymerization of the polymer including equation 8 above Compositions.

The polymer based on 100 parts by weight, the amount of the water can be about about 5000 parts by weight of 400 parts by weight-.Work as institute When stating the amount of water in the range, the polymer can have a good dissolubility, and resultant polymer composition can have it is suitable Together in the viscosity for forming electrode active material layer.

In the polymer of formula 8, the type and amount of the alkali of the alkali metal containing or ammonium can directly affect the alkali metal Or the degree of substitution of ammonium, and particularly, lithium degree of substitution.

The alkali of the alkali metal containing or ammonium can be for selected from lithium hydroxide, potassium hydroxide, sodium hydroxide and ammonium hydroxide It is at least one.

The amount of the alkali of the alkali metal containing or ammonium is adjusted, so that the polymer of the formula 8 based on 1 mole, the alkali gold Belong to or the amount of ammonium is about 0.2 mole -1 mole.When the amount of the alkali metal containing or the alkali of ammonium is 0.2 mole, this meaning As alkali metal or ammonium (such as lithium) in the polymer of the polymer product formula 8 of final product degree of substitution 100% It can be 0.2 under yield.Herein, term yield means by the equation 9 above c polymer indicated or by the formula 9d polymer indicated and containing alkali The reaction yield of reaction between metal or the alkali of ammonium.As described above, the degree of substitution of the alkali metal or ammonium (for example, lithium) It can be determined based on the amount of the alkali for the alkali metal containing or ammonium for being used to prepare polymer.

The reaction of the mixture of the alkali and water of polymer, alkali metal containing or ammonium including formula 9c or 9d, which carries out degree, to lead to Cross the pH confirmation for measuring the reaction mixture.

For example, the pH of the reaction mixture can be about 14 in initial reaction phase, and as reaction can reach directly To 7.5-8.5.Therefore, the pH of the 7.5-8.5 of the reaction mixture can be considered as the termination of reaction.

The amount of the polymer of formula 9c or 9d based on 100 parts by weight, the water in the polymer composition can be about 400 weights About 600 parts by weight of part-are measured, and in embodiments, about 500 parts by weight.When the amount of the water in the range when, the polymerization Compositions can have the appropriate viscosity for coating.

The heat treatment temperature can be for example, about 20 DEG C-about 95 DEG C.When the heat treatment temperature in the range when, can be The degree of substitution of the alkali metal or ammonium (for example, lithium) is easy to control when needing.

The polymer of formula 8 can be obtained and removing water from the polymer composition.Remove water refer to about 80 DEG C- The polymer composition is heat-treated at a temperature of 100 DEG C to be dried.

In some embodiments, when the alkali of the alkali metal containing or ammonium is lithium hydroxide, in subject polymer In formula 8, Y₇And Y₈At least one can be lithium.

In the polymer of formula 8, lithium degree of substitution can be about 0.2- about 1.0, and in some embodiments, about 0.4- is about 1.0。

Term " lithium degree of substitution " is such as given a definition.

When the degree of polymerization of polymer is expressed as d, and there are two the substitution sites for lithium for the first repetitive unit tool of formula 1 When, the sum in the substitution site for lithium in the polymer can be 2d.The expression of lithium degree of substitution is substantially taken by what lithium replaced Subrogate and a little replaces the ratio between site sum 2d with lithium.

When lithium replaces sum 2d in site all to be replaced by lithium, lithium degree of substitution may be defined as 1.For example, 0.56 lithium replaces Degree means that the lithium equal to the quantity of 2d × 0.56 replaces site to be replaced by lithium.

Lithium degree of substitution can be controlled within the required range by adjusting the mixing ratio of the starting material for obtaining polymer. For example, with required lithium degree of substitution lithium replace polymer can by adjust including equation 9 above c or 9d the first repetitive unit and The polymer of substituted or unsubstituted the second repetitive unit of C2-C30 alkylidene and the molar ratio of lithium source (for example, lithium hydroxide) obtain ?.

The degree of substitution of alkali metal or the degree of substitution of ammonium can also be as defined above with respect to described by lithium degree of substitution.

Another embodiment conceived according to the present invention, the electrode for lithium battery include above-mentioned polymer.The electrode It can be manufactured by the following: electrode active material is mixed with the polymer composition for including polymer to prepare electrode active material Composition, and on electrode current collecting body the electrode active material composition is coated and dried to be formed with electrode activity thing The electrode of matter layer.

The electrode can be such as cathode.

The electrode may include the coating and drying of the mixture derived from the polymer composition and electrode active material Product, and for example, by removing water from the polymer composition with comprising the polymer and the electrode active material Product.The drying can about 80 DEG C-about 120 DEG C at a temperature of carry out.

In some other embodiments, other than being used as binders for electrodes, the polymer composition also be can be used Make the coating material of partition or polymer dielectric surface.

The polymer composition can form electrode active material composition when mixing with electrode active material.

The electrode active material and especially as the example of the electrode active material of negative electrode active material be carbonaceous material Material, silicon, Si oxide, the alloy based on silicon, silico-carbo material compound, tin, the alloy based on tin, tin-carbon complex, gold Category oxide, or combinations thereof.

The example of carbonaceous material include crystalline carbon, amorphous carbon, and combinations thereof.The example of the crystalline carbon is graphite, example Such as the natural or artificial graphite of non-shaped, plate, thin slice, spherical shape or fibers form.The example of the amorphous carbon is soft Carbon (carbon being sintered at low temperature), hard carbon, mesophase pitch carbonized product, sintering coke, graphene, carbon black, fullerene cigarette ash, Carbon nanotube, carbon fiber etc..Any suitable carbonaceous material available in the art can be used.

The carbonaceous material may include carbon, graphite or carbon nanotube.

The negative electrode active material can be Si, SiOx (0 < x < 2, for example, x is 0.5-1.5), Sn, SnO₂, siliceous metal Or mixtures thereof alloy,.Can and alloying with silicon with formed silicon alloy metal can for selected from Al, Sn, Ag, Fe, Bi, Mg, Zn, At least one of In, Ge, Pb and Ti.

The negative electrode active material may include can be with the metal/semiconductor metal, its alloy or its oxide of lithium alloyage.Institute Stating can be that (wherein Y is alkali gold to Si, Sn, Al, Ge, Pb, Bi, Sb, Si-Y alloy with the example of the metal/semiconductor metal of lithium alloyage Category, alkaline-earth metal, 13-16 race element, transition metal, rare earth element, or combinations thereof, in addition to Si), (wherein Y is Sn-Y alloy Alkali metal, alkaline-earth metal, 13-16 race element, transition metal, rare earth element, or combinations thereof, in addition to Sn) and MnOx (0 < x≤ 2).Y can for magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf),(Rf), vanadium (V), niobium (Nb), tantalum (Ta),(Db), chromium (Cr), molybdenum (Mo), tungsten (W),(Sg), technetium (Tc), rhenium (Re)、(Bh), iron (Fe), lead (Pb), ruthenium (Ru), osmium (Os),(Hs), rhodium (Rh), iridium (Ir), palladium (Pd), platinum (Pt), Copper (Cu), silver-colored (Ag), golden (Au), zinc (Zn), cadmium (Cd), boron (B), aluminium (Al), gallium (Ga), tin (Sn), indium (In), germanium (Ge), Phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), sulphur (S), selenium (Se), tellurium (Te), polonium (Po), or combinations thereof.The energy and lithium alloy The non-limiting example of the oxide of the metal/semiconductor metal of change is Li-Ti oxide, barium oxide and lithium-barium oxide, SnO₂ With SiOx (0 < x < 2).

For example, the negative electrode active material may include at least one member of 13,14 and 15 elements selected from the periodic table of elements Element.

In some other embodiments, the negative electrode active material may include at least one selected from Si, Ge and Sn Element.

The negative electrode active material can close for carbonaceous material as listed above with selected from silicon, Si oxide and siliceous metal The mixture or compound of gold.

In some embodiments, the negative electrode active material can have a simple particle form, or can be for receiving The nanostructure of meter ruler cun.In some embodiments, the negative electrode active material can have diversified forms such as nanometer Grain, nano wire, nanometer rods, nanotube or nanobelt it is any.

In some embodiments, the negative electrode active material may include the manganese of graphite, Si-CNT compound, nano-scale Oxide (MnOx, 0 < x≤2).

The graphite can have about 0.5 μm-about 2 μm and in some embodiments about 1 μm of average grain diameter.Some In embodiment, the graphite can have the partial size (D90) of about 5 μm-about 7 μm, for example, about 6.5 μm." D90 " as used herein It indicates to correspond to 90% since minimum diameter in the size distribution accumulation curve based on quantity relative to total amount (100%) The partial size of cumulant.

The cathode can manufacture as follows.

For example, the cathode can be by using including negative electrode active material and as binder comprising according to above-mentioned embodiment party The composition of cathode active materials coated collector such as copper foil of the polymer composition of the polymer of either one or two of formula and manufacture.

The negative electrode active material and polymer composition as binder can be mixed described negative to prepare Pole active compound composition.

The polymer composition may include water.The composition of cathode active materials may include conductive agent.

The composition of cathode active materials can be coated on the collector to manufacture cathode.

When manufacturing the cathode, the total amount of the composition of cathode active materials based on 100 parts by weight, the polymerization The amount of polymer in compositions can be about about 30 parts by weight of 1 parts by weight-, and in some embodiments, about 2 parts by weight- About 20 parts by weight.

The coating of the composition of cathode active materials is not limited to specific method, and can be by selected from silk-screen printing, spray It applies, using the coating of scraper, intaglio printing coating, dip-coating, screen printing glue method, the method for smearing and the coating using gap die head It carries out.

In general, the collector may be produced that with about 3 μm-about 20 μm and about 5 μm in embodiments-about 15 μm Thickness.

After being coated on the collector and/or substrate, by the composition of cathode active materials about 80 DEG C-about (heating for the first time) dry at 120 DEG C to remove solvent, then roll-in is subsequently dried to obtain the cathode.

When for removing the drying temperature in the first time heating for being used as the water of solvent from the electrode in the range When, it can inhibit and generate bubble on the electrode surface, so that can get the electrode with improved surface uniformity.It is described dry It is dry to be carried out in atmospheric conditions.

It can be second of heating in a vacuum after the first time heating.Second heating can about 100 DEG C- About 1 × 10 at a temperature of about 200 DEG C^-4About 1 × 10^-6It is carried out under the vacuum of support.

The non-limiting example of the conductive agent is acetylene black, Ketjen black, natural graphite, artificial graphite, carbon black, carbon fiber Dimension, metal powder and metallic fiber such as copper, nickel, aluminium or silver, polyphenylene derivatives or its at least two mixture.It can Use available any conductive agent in the art.

In addition to above-mentioned binder, the cathode can further comprise widely used common bond in the art. The non-limiting example of the common bond is sodium carboxymethylcellulose (" Na-CMC "), alginic acid derivative, chitosan spread out Biology, polyvinyl alcohol (" PVA "), polyacrylic acid (" PAA "), Sodium Polyacrylate (" Na-PAA "), polyvinylpyrrolidone (" PVP "), polyacrylamide, vinylidene/hexafluoropropylene copolymer (" P (VDF-HFP) "), gather inclined fluorine at polyamidoimide Ethylene (" PVDF "), polyacrylonitrile (" PAN "), aqueous dispersion type butadiene-styrene rubber (" SBR "), aqueous dispersion type butadiene rubber (" BR "), its modified product in main chain (for example, fluorinated polymer or have sulfone (- SO₂) substituent group polymer) or Its copolymer (for example, random copolymer, block copolymer or alternate copolymer with other polymer).

The collector is not particularly limited, and can be any material, as long as it is with suitable electric conductivity, without in institute Cause chemical change in the battery of manufacture.The example of the collector be copper, stainless steel, aluminium, nickel, titanium, be sintered carbon, with carbon, nickel, The copper or stainless steel and aluminium-cadmium alloy of titanium or silver surface processing.

Have tiny irregularity to enhance the collector pair on the surface thereof in addition, the collector can be processed into The adherency of the negative electrode active material, and may include a variety of of film, piece, foil, net, cell structure, foams and non-woven fleece Any use of form.

When the electrode is anode, compound (the lithiumation intercalation chemical combination for allowing reversible insertion and the deintercalation of lithium can be used Object) as a positive electrode active material.The positive active material may include selected from lithium and cobalt oxides, lithium nickel cobalt manganese oxide, lithium nickel At least one of cobalt aluminum oxide, lithium iron phosphate oxide and lithium manganese oxide.The positive active material is not limited to these examples, It and can be available any positive active material in the art.

For example, the positive active material can be at least one chosen from the followings: lithium and cobalt oxides (LiCoO₂)；Lithium nickel oxygen Compound (LiNiO₂)；Lithium manganese oxide, including Li_1+xMn_2-xO₄(wherein x is 0-0.33), Li₂MnO₃、LiMn₂O₄And LiMnO₂； Lithium Cu oxide (Li₂CuO₂)；Oxide/lithium ferrite (LiFe₃O₄)；Lithium-barium oxide (LiV₃O₈)；Copper barium oxide (Cu₂V₂O₇)； Barium oxide (V₂O₅)；Lithium nickel oxide (LiNi_1-xM_xO₂, wherein M is Co, Mn, Al, Cu, Fe, Mg, B or Ga；It is with x 0.01-0.3)；Lithium manganese oxide, including LiMn_2-xM_xO₂(wherein M is Co, Ni, Fe, Cr, Zn or Ta；It is 0.01-0.1 with x) And Li₂Mn₃MO₈(wherein M is Fe, Co, Ni, Cu or Zn)；Wherein lithium is by the partially substituted lithium manganese oxide of alkaline-earth metal ions (LiMn₂O₄)；Di-sulphide compounds；With iron and molybdenum oxides (Fe₂(MoO₄)₃)。

For example, the positive active material can be the compound indicated by one of following formula: Li_aA_1-bB_bD₂(wherein 0.90≤a ≤ 1.8 and 0≤b≤0.5)；Li_aE_1-bB_bO_2-cD_c(wherein 0.90≤a≤1.8,0≤b≤0.5 and 0≤c≤0.05)；LiE_{2- b}B_bO_4-cD_c(wherein 0≤b≤0.5 and 0≤c≤0.05)；Li_aNi_1-b-cCo_bB_cD_α(wherein 0.90≤a≤1.8,0≤b≤0.5, 0≤c≤0.05 and 0 < α≤2)；Li_aNi_1-b-cCo_bB_cO_2-αF_α(the He of wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 0<α<2)；Li_aNi_1-b-cCo_bB_cO_2-αF_α(wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 and 0 < α < 2)； Li_aNi_1-b-cMn_bB_cD_α(wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 and 0 < α≤2)；Li_aNi_1-b-cMn_bB_cO_2-α F_α(wherein 0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05 and 0 < α < 2)；Li_aNi_1-b-cMn_bB_cO_2-αF_α(wherein 0.90≤ A≤1.8,0≤b≤0.5,0≤c≤0.05 and 0 < α < 2)；Li_aNi_bE_cG_dO₂(wherein 0.90≤a≤1.8,0≤b≤0.9,0≤ C≤0.5 and 0.001≤d≤0.1)；Li_aNi_bCo_cMn_dG_eO₂(wherein 0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0 ≤ d≤0.5 and 0.001≤e≤0.1)；Li_aNiG_bO₂(wherein 0.90≤a≤1.8 and 0.001≤b≤0.1)；Li_aCoG_bO₂ (wherein 0.90≤a≤1.8 and 0.001≤b≤0.1)；Li_aMnG_bO₂(wherein 0.90≤a≤1.8 and 0.001≤b≤0.1)；

Li_aMn₂G_bO₄(wherein 0.90≤a≤1.8 and 0.001≤b≤0.1)；QO₂；QS₂；LiQS₂；V₂O₅；LiV₂O₅； LiIO2；LiNiVO4；Li(3_-F) J2 (PO4) 3 (wherein 0≤f≤2)；Li(3_-F) Fe2 (PO4) 3 (wherein 0≤f≤2)；With LiFePO₄。

In above formula, A be selected from nickel (Ni), cobalt (Co), manganese (Mn), and combinations thereof；B is selected from aluminium (Al), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), rare earth element, and combinations thereof；D is selected from oxygen (O), fluorine (F), sulphur (S), phosphorus (P), and combinations thereof；E be selected from cobalt (Co), manganese (Mn), and combinations thereof；F be selected from fluorine (F), sulphur (S), phosphorus (P), And combinations thereof；G be selected from aluminium (Al), chromium (Cr), manganese (Mn), iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce), strontium (Sr), vanadium (V), And combinations thereof；Q be selected from titanium (Ti), molybdenum (Mo), manganese (Mn), and combinations thereof；I be selected from chromium (Cr), vanadium (V), iron (Fe), scandium (Sc), Yttrium (Y), and combinations thereof；With J be selected from vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), and combinations thereof.

Compound as a positive electrode active material listed above can have surface coating layer (hereinafter, " clad "). Alternatively, can be used the compound without clad and the compound with clad mixture, the compound be selected from On the compound enumerated.The clad may include the compound of at least one cladding element chosen from the followings: coat element Oxide, hydroxide, oxyhydroxide, carbonic acid oxonium salt and hydroxyl carbonate.Compound for the clad can be nothing It is setting or crystallization.For the clad cladding element can for magnesium (Mg), aluminium (Al), cobalt (Co), potassium (K), sodium (Na), Calcium (Ca), silicon (Si), titanium (Ti), vanadium (V), tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr) or its mixing Object.The clad can be used any compound including these elements listed above according to when using the cladding element Any suitable method that the physical property of positive active material adversely affects is not formed when compound.For example, described Any known spraying of ordinary skill, dipping or other methods can be used to be formed for clad.The positive active material Non-limiting example be LiNiO₂、LiCoO₂、LiMn_xO_2x(wherein x=1,2), LiNi_1-xMn_xO₂(wherein 0 < x < 1), LiNi_1-x-yCo_xMn_yO₂(it is 0-0.5 that wherein x, which is 0-0.5 and y), LiFeO₂、V₂O₅, TiS and MoS.

As the binder for anode, the polymer composition according to above embodiment can be used.The binder It is bonded to each other strongly positive active material particle and positive active material particle is made to be firmly bonded to collector.As allusion quotation The example of type, the binder can be following at least one: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diethyl Atriacetyl cellulose, polyvinyl chloride, carboxylation polyvinyl chloride, polyvinyl fluoride, the oxygen containing ethylidene polymer, polyvinylpyrrolidone Ketone, polyurethane, polytetrafluoroethylene (PTFE), Kynoar, polyethylene, polypropylene, butadiene-styrene rubber (" SBR "), polyamidoimide, third (acrylic modified) SBR, epoxy resin and the nylon that olefin(e) acid (ester) is changed, but not limited to this.

When preparing the positive electrode active compound composition, it can be used and used in the composition of cathode active materials Identical conductive agent.

The positive active material, binder and conductive agent can be mixed to obtain positive electrode active material layer combination Object.

When the polymerization when forming positive electrode active material layer using the one or more embodiments conceived according to the present invention When compositions are as binder, do not need using solvent.

When using common positive electrode binder when forming positive electrode active material layer, solvent can be used.The solvent it is non- Limitative examples are water, dimethyl sulfoxide (" DMSO "), N,N-dimethylformamide (" DMF "), DMAC N,N' dimethyl acetamide (" DMA "), tetrahydrofuran (" THF "), 1,4- dioxane, 1,2- dimethoxy-ethane (" DME ") and N-Methyl pyrrolidone (“NMP”)。

The anode using the positive electrode active compound composition can be manufactured with identical mode in the manufacture of the cathode, Other than using the positive active material to replace the negative electrode active material.

The amount of the positive active material, conductive agent and solvent can be usually used in the manufacture of lithium battery in this field Those of level.According to the purposes and structure of lithium battery, at least one of conductive agent and solvent can not used.If desired, Any kind of various additives such as dispersing agent, thickener or filler can be further used in the manufacture of anode.

Another embodiment conceived according to the present invention, lithium battery include that above-mentioned cathode, anode, partition and packet are containing lithium salt Nonaqueous electrolyte.

The partition may be provided between the anode and cathode.The partition can be for high ion permeability and by force Mechanical strength insulation film.

The partition can have the aperture of about 0.01 μm-about 10 μm and about 1 μm in embodiments-about 10 μm, Yi Jiyue 5 μm-about 20 μm and about 10 μm in embodiments-about 15 μm of thickness.The example of the partition is the polymer based on alkene Such as polyethylene, polypropylene, polybutene, and the piece made of glass fibre or polyethylene or non-woven fleece.When electric using solid When solving matter such as polymer dielectric as electrolyte, the solid electrolyte can also serve as partition.

The partition can be single layer or polymer including at least two based on alkene such as polyethylene, polypropylene, poly- inclined Vinyl fluoride, or combinations thereof layer multilayer.The multilayer can be hybrid multilayer.For example, the partition can be include polyethylene and The double-layer clapboard of polypropylene layer, three layers of partition including polyethylene, polypropylene and polyethylene layer, or including polypropylene, polyethylene With three layers of partition of polypropylene layer.

The packet nonaqueous electrolyte containing lithium salt may include nonaqueous electrolyte matrix and lithium salts.

The nonaqueous electrolyte matrix can be Nonaqueous liquid solvents, organic solid electrolyte matrix or inorganic solid electrolyte Matter matrix.

The non-limiting example of the Nonaqueous liquid solvents is any following: aprotic organic solvent such as N- methyl- 2-Pyrrolidone, propylene carbonate, ethylene carbonate (" EC "), butylene carbonate, dimethyl carbonate, diethyl carbonate (" DEC "), gamma-butyrolacton, 1,2- dimethoxy-ethane (" DME "), tetrahydrofuran (" THF "), 2- methyltetrahydrofuran (" 2- Methyl-THF "), dimethyl sulfoxide (" DMSO "), 1,3- dioxolanes, 1,4- dioxane, formamide, N,N-dimethylformamide (" DMF "), DMAC N,N' dimethyl acetamide (" DMA "), acetonitrile, nitroethane, methyl formate, methyl acetate, phosphotriester, front three Oxygroup methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3- dimethyl -2- imidazolidinone, propylene carbonate spread out Biology, tetrahydrofuran derivatives, ether, methyl propionate, ethyl propionate and fluoroethylene carbonate (" FEC ").

The non-limiting example of the organic solid electrolyte matrix be polythene derivative, polyethylene oxide derivatives, Polypropylene oxide derivatives, phosphate ester polymer, polyester sulfide, polyvinyl alcohol, Kynoar and include ionic dissociation base The polymer of group.

The non-limiting example of the inorganic solid electrolyte matrix is Li₃N、LiI、Li₅NI₂、Li₃N-LiI-LiOH、 Li₂SiS₃、Li₄SiO₄、Li₄SiO₄- LiI-LiOH and Li₃PO₄-Li₂S-SiS₂。

The lithium salts can be any lithium salts being dissolvable in water in above-mentioned nonaqueous electrolyte matrix.The lithium salts it is non-limiting Example is LiCl, LiBr, LiI, LiClO₄、LiBF₄、LiB₁₀Cl₁₀、LiPF₆、LiCF₃SO₃、LiCF₃CO₂、LiAsF₆、LiSbF₆、 LiAlCl₄、CH₃SO₃Li、(CF₃SO₂)₂NLi, chloroboric acid lithium, lower alphatic carboxylic acid lithium and tetraphenylboronic acid lithium.It is filled to improve Electricity/flash-over characteristic or anti-flammability, the nonaqueous electrolyte can be to be further added with, for example, pyridine, triethyl phosphite, three Ethanol amine, cyclic ethers, ethylenediamine, n- glycol dimethyl ether, hexamethylphosphoric triamide, nitrobenzene derivative, sulphur, quinine imines Dyestuff, N- replace oxazolidone, N, N- replace imidazoline, glycol dialkyl ether, ammonium salt, pyrroles, 2-methyl cellosolve or Aluminium chloride.In some other embodiments, in order to provide flame resistance, halogen-containing solvent such as tetrachloro can be further used Change carbon and trifluoro-ethylene.Referring to Fig.1, the lithium battery 1 for the embodiment conceived according to the present invention includes anode 3, cathode 2 and partition 4.It by anode 3, cathode 2 and the winding of partition 4 or folds, is then sealed in battery case 5.Then, battery case 5 is used into organic electrolysis Matter solution fills and cap assembly 6 is used to seal, and thus completes the manufacture of lithium battery 1.Battery case 5 can be cylindrical type, square type or film Type.For example, lithium battery 1 can be film type battery.Lithium battery 1 can be lithium ion battery.

Lithium battery 1 can be the lithium ion battery with about 4.3V or bigger charging voltage.

Partition 4 can be between anode 3 and cathode 2 to form battery component.Alternatively, the battery component can double units Battery structure is stacked and is impregnated with electrolyte solution.Gains are placed in in bag and gas-tight seal, thus completion lithium ion polymerization The manufacture of object battery.

Alternatively, can stack multiple battery components to form battery pack, can be used for running and needing high at high temperature In any device of output, for example, being used in laptop computer, smart phone, electric vehicle etc..

Lithium battery 1 can have improved high-rate characteristics and life characteristic, and therefore can be applied to electric vehicle (" EV ") example In hybrid electric vehicle such as plug-in hybrid-power electric vehicle (" PHEV ").

Substituent group in above formula can such as give a definition.

Term " alkyl " as used in this article indicate to derive from fully saturated, branching or it is nonbranched (or straight chain or Line style) hydrocarbon and with defined carbon atom number monoradical.

The non-limiting example of " alkyl " is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding Base, tert-butyl, isopentyl, neopentyl, n-hexyl, 3- methylhexyl, 2,2- dimethyl amyl group, 2,3- dimethyl amyl group and positive heptan Base.

At least one hydrogen atom of the alkyl can be replaced as follows: halogen atom, the C1-C30 being substituted with halogen atoms Alkyl is (for example, CCF₃、CHF₂、CH₂F、CCl₃Deng), C1-C30 alkoxy, C2-C30 alkoxyalkyl, hydroxyl (- OH), nitro (-NO₂), cyano (- CN), amino (- NRR ', wherein R and R ' independently is hydrogen or C1-C30 alkyl), acylamino- (- C (=O) NRR ', wherein R and R ' independently is hydrogen or C1-C30 alkyl), (- NHNRR ', wherein R and R ' independently is hydrogen or C1- to diazanyl C30 alkyl), hydrazone group (- CR=NHNR ' R ", wherein R, R ' independently be hydrogen or C1-C30 alkyl with R "), azido (- N₃), amidine Base (- C (=NH) NRR ', wherein R and R ' independently is hydrogen or C1-C30 alkyl), carboxyl (- CO₂) or its salt, sulfonyl, ammonia sulphur H Acyl group, sulfonic group (- SO₃) or its salt, phosphate (- P (=O) (OH) H₂) or its salt, C1-C30 alkyl, C2-C30 alkenyl, C2- C30 alkynyl, C1-C30 miscellaneous alkyl, C6-C30 aryl, C7-C30 aralkyl, C2-C30 heteroaryl, C3-C30 heteroarylalkyl, C2- C30 heteroaryloxy, C3-C30 Heteroaryloxyalkyl or C6-C30 heteroaryl alkoxy.

Term " halogen atom " as used in this article indicates fluorine, bromine, chlorine, iodine etc..

Term " the C1-C30 alkyl being substituted with halogen atoms " as used in this article is indicated by least one halogen atom Substituted C1-C30 alkyl.The non-limiting example of the C1-C30 alkyl replaced by least one halogen atom is monohaloalkyl Alkyl or multi-haloalkyl, including dihalo alkyl or whole haloalkyl.

Term " monohaloalkyl alkyl " as used in this article indicates the alkyl including an iodine, bromine, chlorine or fluorine atom.Term " dihalo alkyl " and " multi-haloalkyl " indicates the alkyl including at least two identical or different halogen atoms.Term is " complete Halogenated alkyl " indicates the alkyl that wherein all hydrogen atoms are all replaced by identical or different halogen atom.

Term " naphthenic base " as used in this article indicates only full with carboatomic ring atom and with defined carbon atom number With hydrocarbon ring group.The non-limiting example of naphthenic base includes cyclohexyl.

Term " alkenyl " as used in this article indicates to derive from linear chain or branched chain aliphatic hydrocarbon, has at least one double bond and tool There is the monoradical of defined carbon atom number.The non-limiting example of the alkenyl include vinyl, acrylic, isopropenyl and Hexenyl.At least one hydrogen atom of the alkenyl can by with those listed identical substituent group generation above with respect to alkyl It replaces.

Term " alkynyl " as used in this article indicates to derive from linear chain or branched chain aliphatic hydrocarbon, has at least one three key and tool There is the monoradical of defined carbon atom number.The non-limiting example of the alkynyl includes acetenyl and propinyl.The alkynyl At least one hydrogen atom can be replaced with those listed identical substituent group above with respect to alkyl.

Term " alkoxy " expression " alkyl-O- " as used in this article, wherein the alkyl with it is described above identical And there is defined carbon atom number.The non-limiting example of the alkoxy includes methoxyl group, ethyoxyl, propoxyl group, the third oxygen of 2- Base, butoxy, tert-butoxy, amoxy and hexyloxy.At least one hydrogen atom of the alkoxy can by with above with respect to alkane Those listed identical substituent group of base replaces.

Term " aryl " (it is used alone or in combination) as used in this article indicates to derive from the virtue comprising at least one ring Race's hydrocarbon and the monoradical with defined carbon atom number.

Term " aryl " as used in this article is construed to include the aromatic ring at least one cycloalkyl ring is fused to Group.

The non-limiting example of " aryl " includes phenyl, naphthalene and tetralyl.

At least one hydrogen atom of " aryl " can by with those listed identical substituent group above with respect to alkyl Instead of.

Term " aralkyl " as used in this article indicates alkyl be substituted with aryl and with defined carbon atom number. The non-limiting example of " aralkyl " includes benzyl, phenyl-CH₂CH₂Etc..

Term " aryloxy group " as used in this article indicates "-O- the aryl " with defined carbon atom number.The virtue oxygen The non-limiting example of base is phenoxy group.At least one hydrogen atom of " aryloxy group " can by with above with respect to cited by alkyl Those of identical substituent group replace.

It includes selected from nitrogen (N), oxygen (O), phosphorus (P) and sulphur (S) that term " heteroaryl " as used in this article, which indicates to derive from, The monocycle or bicyclic aromatic organic compound of at least one hetero atom (wherein the remainder of annular atom is carbon) and there is regulation Carbon atom number monoradical.The heteroaryl may include such as one to five hetero atom, and in some embodiments, can Including five to ten-ring.

In the heteroaryl, S or N can exist with various oxidised forms.

The non-limiting example of bicyclic heteroaryl includes thienyl, furyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazole Base, isothiazolyl, 1,2,3-Di azoly, 1,2,4-Di azoly, 1,2,5-Di azoly, 1,3,4-Di azoly, 1, 2,3- thiadiazolyl group, 1,2,4- thiadiazolyl group, 1,2,5- thiadiazolyl group, 1,3,4- thiazolyl, isothiazole -3- base, isothiazole -4- Base, isothiazole -5- base,Azoles -2- base,Azoles -4- base,It is azoles -5- base, differentIt is azoles -3- base, differentAzoles -4- base, isoxazole - 5- base, 1,2,4- triazole -3- base, 1,2,4- triazole -5- base, 1,2,3- triazole-4-yl, 1,2,3- triazole -5- base, tetrazole radical, Pyridine -2- base, pyridin-3-yl, 2- pyrazine -2- base, pyrazine -4- base, pyrazine -5- base, 2- pyrimidine -2-base, 4- pyrimidine -2-base, With 5- pyrimidine -2-base.

Term " heteroaryl " as used in this article is construed to include being fused to aryl, cycloaliphatic groups and heterocyclic group The heteroaromatic rings of at least one.

The non-limiting example of bicyclic heteroaryl is indyl, isoindolyl, indazolyl, indolizine base, purine radicals, quinolizine Base, quinolyl, isoquinolyl, cinnoline base, phthalazinyl, naphthyridines base, quinazolyl, quinoxalinyl, phenanthridinyl, phenanthroline, pheno Piperazine base, phenothiazinyl, phenoPiperazine base, benzisoquinoline base, thieno [2,3-b] furyl, furans simultaneously [3,2-b]-pyranose, 5H- pyrido [2,3-d]-o-Piperazine base, 1H- pyrazolo [4,3-d]-Oxazolyl, 4H- imidazo [4,5-d] thiazolyl, pyrrole Piperazine simultaneously [2,3-d] pyridazinyl, imidazo [2,1-b] thiazolyl, imidazo [1,2-b] [1,2,4] triazine radical, 7- benzo [b] thiophene Pheno base, benzoOxazolyl, benzimidazolyl, benzothiazolyl, benzo oxygen azepineBase, benzoPiperazine base, 1H- pyrrolo- [1,2-b] [2] benzo-azaBase, benzofuranyl, benzothienyl, benzotriazole base, pyrrolo- [2,3-b] pyridyl group, Pyrrolo- [3,2-c] pyridyl group, pyrrolo- [3,2-b] pyridyl group, imidazo [4,5-b] pyridyl group, imidazo [4,5-c] pyridine Base, pyrazolo [4,3-d] pyridyl group, pyrazolo [4,3-c] pyridyl group, pyrazolo [3,4-c] pyridyl group, pyrazolo [3,4-d] Pyridyl group, pyrazolo [3,4-b] pyridyl group, imidazo [1,2-a] pyridyl group, pyrazolo [1,5-a] pyridyl group, pyrrolo- [1, 2-b] pyridazinyl, imidazo [1,2-c] pyrimidine radicals, pyrido [3,2-d] pyrimidine radicals, pyrido [4,3-d] pyrimidine radicals, pyrido It is [3,4-d] pyrimidine radicals, pyrido [2,3-d] pyrimidine radicals, pyrido [2,3-b] pyrazinyl, pyrido [3,4-b] pyrazinyl, phonetic Pyridine simultaneously [5,4-d] pyrimidine radicals, pyrazine simultaneously [2,3-b] pyrazinyl and pyrimido [4,5-d] pyrimidine radicals.

At least one hydrogen atom of " heteroaryl " can by with those listed identical substitution above with respect to alkyl Base replaces.

It is that term " heteroarylalkyl " expression as used in this article is substituted by heteroaryl and with defined carbon atom number Alkyl.The non-limiting example of the heteroarylalkyl includes (pyridine -2- base) methyl (C₅H₄NCH₂)。

Term " heteroaryloxy " as used in this article indicates the-O- heteroaryl moieties with defined carbon atom number.Institute At least one hydrogen atom for stating heteroaryloxy can be replaced with those listed identical substituent group above with respect to alkyl.It is described The non-limiting example of heteroaryloxy includes (pyridine -2- base) oxygroup (C₅H₄NO)。

Term " carbocyclic ring " group as used in this article indicates the unit price saturation with defined carbon atom number or part not The non-aromatic monocyclic of saturation, bicyclic or tricyclic hydrocarbyl.

The non-limiting example of monocycle alkyl includes cyclopenta, cyclopentenyl, cyclohexyl and cyclohexenyl group.

The non-limiting example of bicyclic alkyl includes bornyl, decahydro naphthalene, bicyclic [2.1.1] hexyl, bicyclic [2.2.1] Heptyl, bicyclic [2.2.1] heptenyl and bicyclic [2.2.2] octyl.

The non-limiting example of tricyclic hydrocarbyl is adamantyl.

At least one hydrogen atom of " carbon ring group " can by with above with respect to alkyl, those listed identical is taken Dai Ji is replaced.

It is that term " carbocylic radical alkyl " as used in this article indicates to be replaced by carbon ring group and with defined carbon atom Several alkyl.The non-limiting example of the carbocylic radical alkyl includes cyclohexyl methyl.

Term " heterocyclic group " as used in this article, which indicates, to be included hetero atom such as N, S, P or O and has defined carbon Five to ten yuan of carbon ring groups of atomicity.The non-limiting example of the heterocyclic group is pyrrolidinyl and piperidyl.It is described miscellaneous At least one hydrogen atom in cyclic group can be replaced with those listed identical substituent group above with respect to alkyl.

Term " heterocyclylalkyl group " as used in this article indicates to be replaced by heterocyclic group and the carbon with specified quantity is former The alkyl of son.The non-limiting example of the Heterocyclylalkyl includes (piperidin-2-yl) methyl (C₅H₉NCH₂)。

It is that term " Heteroaryloxyalkyl " expression as used in this article is replaced by heteroaryloxy and former with defined carbon The alkyl of subnumber.The non-limiting example of the Heteroaryloxyalkyl includes (pyridine -2- base) oxygroup methyl (C₅H₄NOCH₂)。

Term " heteroaryl alkoxy " expression "-O- heteroarylalkyl " as used in this article.The non-limit of the heteroaryl alkoxy Property example processed includes (pyridine -2- base) methyl oxygroup (C₅H₄NCH₂O)。

Term " sulfonyl " indicates R "-SO₂, wherein R " is hydrogen atom, alkyl, aryl, heteroaryl, aralkyl, heteroaryl alkane Base, alkoxy, aryloxy group, naphthenic base or heterocyclic group.

Term " sulfonamides " basis representation H₂NS(O₂)-, alkyl-NHS (O₂)-, (alkyl)₂NS(O₂)-, aryl-NHS (O₂)-、 Alkyl-(aryl)-NHS (O₂)-, (aryl)₂NS(O)₂, heteroaryl-NHS (O₂)-, (aryl-alkyl)-NHS (O₂)-or (heteroaryl Base-alkyl)-NHS (O₂)-。

Term " amino " indicates that wherein nitrogen-atoms is covalently bound at least one carbon or heteroatomic group.The amino can Refer to for example optionally substituted-NH₂Group.

Term " amino " is also represented by wherein nitrogen and is integrated at least one other alkyl with defined carbon atom number " alkyl amino " and wherein nitrogen-atoms are integrated to the " virtue of one or two selected aryl with defined carbon atom number Base amino " and " ammonia diaryl base ".

Term " alkylidene " as used in this article indicates the straight chain with defined carbon atom number or branched divalent aliphatic series Alkyl.The non-limiting example of the alkylidene includes methylene, ethylidene, propylidene and butylidene.

Term " alkenylene " as used in this article indicates at least one carbon-to-carbon double bond and has defined carbon atom Several linear chain or branched chain bivalent hydrocarbon radicals.The non-limiting example of the alkenylene includes allylidene.

Term " alkynylene " as used in this article indicates at least one carbon-carbon triple bond and has defined carbon atom Several linear chain or branched chain bivalent hydrocarbon radicals.The non-limiting example of the alkynylene includes sub- propinyl.

Term " cycloalkylidene " as used in this article refers to the cyclic divalent aliphatic hydrocarbyl with defined carbon atom number. The non-limiting example of the cycloalkylidene includes sub- cyclopropanyl, sub- cyclobutane base, cyclopentenylidene and cyclohexadienylidene.

One or more embodiments are more fully described now with reference to following embodiment.However, these embodiments are only It is for the purpose of illustration and is not intended to limit the range of one or more of embodiments.

In following preparation embodiment, term " poly- (isobutene-alt- maleic anhydride) and the poly- { (Malaysia isobutene-alt- Acid anhydrides)-co- (isobutene-alt- maleic acid lithium salts) " in " alt " and " co " be respectively intended to mean alternating polymer and copolymer.

It prepares embodiment 1: including poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (the lithium degree of substitution: preparation 0.8) of (hereinafter, Li-0.8-PIBMA)

Poly- (isobutene-alt- maleic anhydride) (mixing with isobutene and maleic anhydride that 4g is indicated by following formula 8c Than=1:1, by mol；With weight average molecular weight=about 300,000~350,000) and 0.996g lithium hydroxide (LiOH) be added to It in 96g deionized water, then mixes to obtain mixture, then by the mixture stir about 24 hours at about 70 DEG C To prepare poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } including following formula 8a (below In, the polymer of formula 8a) and deionized water polymer composition.

The composition of the polymer comprising formula 8a based on 100 parts by weight, the amount of the polymer of formula 8a are about 5 parts by weight.

Formula 8c

The polymer composition is filtered to remove water-msoluble ingredients.Water is removed from filtered solid product, so It is dried at about 80 DEG C afterwards to obtain the polymer of following formula 8a.

The polymer of formula 8a is with about 0.8 lithium degree of substitution and the weight average molecular weight of about 300,000- about 350,000.

[formula 8a]

In formula 8a, indicate that a of molar fraction and b may respectively be 0.2 and 0.8.

It prepares embodiment 2: including the group of poly- (isobutene-alt- maleic acid lithium salts) (hereinafter, Li-1.0-PIBMA) Close object (lithium degree of substitution: preparation 1.0)

Poly- (isobutene-alt- maleic acid lithium salts) including formula 8b is prepared in the same manner as in example 1 (below In, the polymer of formula 8b) and deionized water polymer composition, other than using 1.245gLiOH and 96g deionized water.

In the polymer composition, the composition of the polymer comprising formula 8b based on 100 parts by weight, formula 8b's is poly- The amount for closing object is about 5 parts by weight.

The polymer composition is filtered to remove water-msoluble ingredients.Water is removed from filtered solid product, so It is dried at about 80 DEG C afterwards to obtain the polymer of following formula 8b.

The polymer of following formula 8b is with about 1.0 lithium degree of substitution and the weight average molecular weight of about 300,000- about 350,000.

Formula 8b

It prepares embodiment 3: including poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (the lithium degree of substitution: preparation 0.5) of (hereinafter, Li-0.5-PIBMA)

Prepare in the same manner as in example 1 including formula 8a poly- { (isobutene-alt- maleic anhydride)-co- is (different Butylene-alt- maleic acid lithium salts) } polymer composition of (hereinafter, polymer of formula 8a) and deionized water, in addition to using Except 0.623g LiOH and 96g deionized water.It is poly- comprising formula 8a based on 100 parts by weight in the polymer composition The composition of object is closed, the amount of the polymer of formula 8a is about 5 parts by weight.

The polymer composition is filtered to remove water-msoluble ingredients.Water is removed from filtered solid product, so It is dried at about 80 DEG C afterwards to obtain the polymer of following formula 8a.

The polymer of following formula 8a is with about 0.5 lithium degree of substitution and the weight average molecular weight of about 300,000- about 350,000.

Formula 8a

In formula 8a, a and b can be respectively 0.5 molar fraction.

It prepares embodiment 4: including poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (the lithium degree of substitution: preparation 0.6) of (hereinafter, Li-0.6-PIBMA)

It is prepared in the same manner as in example 1 including poly- { (isobutene-alt- maleic anhydride)-co- (isobutene- Alt- maleic acid lithium salts) } polymer composition of (hereinafter, polymer of formula 8a) and deionized water, in addition to using 0.747g Except LiOH and 96g deionized water.In the polymer composition, the polymer comprising formula 8a based on 100 parts by weight Composition, the amount of the polymer of formula 8a are about 5 parts by weight.

The polymer composition is filtered to remove water-msoluble ingredients.Water is removed from filtered solid product, so It is dried at about 80 DEG C afterwards to obtain the polymer of following formula 8a.

The polymer of formula 8a is with about 0.6 lithium degree of substitution and the weight average molecular weight of about 300,000- about 350,000.

Formula 8a

In formula 8a, indicate that a of molar fraction and b may respectively be 0.4 and 0.6.

It prepares embodiment 5: including poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (the lithium degree of substitution: preparation 0.7) of (hereinafter, Li-0.7-PIBMA)

Prepare in the same manner as in example 1 including formula 8a poly- { (isobutene-alt- maleic anhydride)-co- is (different Butylene-alt- maleic acid lithium salts) } polymer composition of (hereinafter, the polymer of formula 8a) and deionized water, in addition to using Except 0.873g LiOH and 96g deionized water.

In the polymer composition, the composition of the polymer comprising formula 8a based on 100 parts by weight, formula 8a's is poly- The amount for closing object is about 5 parts by weight.

The polymer composition is filtered to remove water-msoluble ingredients.Water is removed from filtered solid product, so It is dried at about 80 DEG C afterwards to obtain the polymer of following formula 8a.

The polymer of formula 8a is with about 0.7 lithium degree of substitution and the weight average molecular weight of about 300,000- about 350,000.

Formula 8a

In formula 8a, a can be 0.3 molar fraction and b can be 0.7 molar fraction.

It prepares embodiment 6: including poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (the lithium degree of substitution: preparation 0.2) of (hereinafter, Li-0.2-PIBMA)

Prepare in the same manner as in example 1 including formula 8a poly- { (isobutene-alt- maleic anhydride)-co- is (different Butylene-alt- maleic acid lithium salts) } polymer composition of (hereinafter, polymer of formula 8a) and deionized water, in addition to using Except 0.250g LiOH and 96g deionized water.It is poly- comprising formula 8a based on 100 parts by weight in the polymer composition The composition of object is closed, the amount of the polymer of formula 8a is about 5 parts by weight.

The polymer composition is filtered to remove water-msoluble ingredients.Water is removed from filtered solid product, so It is dried at about 80 DEG C afterwards to obtain the polymer of following formula 8a.

The polymer of formula 8a is with about 0.2 lithium degree of substitution and the weight average molecular weight of about 300,000- about 350,000.

Formula 8a

In formula 8a, a can be 0.8 molar fraction and b can be 0.2 molar fraction.

It prepares embodiment 7: including poly- { (isobutene-alt- maleic anhydride)-co- (Malaysia isobutene-alt- acid ammonium salt) } Composition preparation

Poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid ammonium that 10g is indicated by following formula 9 Salt) } (have about 160,000-170,000 weight average molecular weight) (hereinafter, the polymer of formula 9) and 90g deionized water mix Merging be stirred at room temperature about 24 hours with obtain include poly- { (isobutene-alt- the maleic anhydride)-co- indicated by following formula 9 (Malaysia isobutene-alt- acid ammonium salt) } (having about 160,000-170,000 weight average molecular weight) (hereinafter, formula 9 is poly- Close object) and deionized water polymer composition.

Formula 9

The polymer of the formula 9 has about 1,000- about 1, and 200 degree of polymerization, wherein a in formula 9 is that 0.2 and b is 0.8。

The polymer composition of the polymer comprising formula 9 based on 100 parts by weight, the formula 9 in the polymer composition The amount of polymer be about 10 parts by weight.

Preparation embodiment 8: (have comprising poly- { (ethylene-alt- maleic anhydride)-co- (ethylene-alt- maleic acid lithium salts) } 0.5 lithium degree of substitution) (hereinafter, referred to as Li-0.5-PEMA) composition

By 10g poly- (ethylene-co-maleic anhydride) (with 1:1 ethylene and maleic anhydride mole mixture ratio and 400, 000 weight average molecular weight) and 1.9g LiOH mixed in 90g deionized water, then at about 70 DEG C stir about 24 hours to obtain Poly- { (ethylene-alt- maleic anhydride)-co- (ethylene-alt- maleic acid lithium salts) } that is indicated by following formula 10 (hereinafter, formula 10 Polymer) polymer composition in deionized water.

The polymer of formula 10 in the polymer composition has about 0.5 lithium degree of substitution.Packet based on 100 parts by weight The polymer composition of the polymer of formula 10 is included, the polymer of formula 10 is about 10 parts by weight.

Formula 10

In formula 10, indicate both a and b of molar fraction can be 0.5.The polymer of formula 10 with about 3,000 it is poly- It is right.

Embodiment 1: the manufacture of cathode and coin half-cell battery

Using 4.5g as graphite (SFG6) powder (being available from Timcal Co.) (D90=about 6.5 μm) of negative electrode active material With 10g as binder preparation embodiment 1 include poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- horse Carry out sour lithium salts) } (lithium degree of substitution: composition 0.8) is mixed with the weight ratio of 90:10 to prepare slurry.

The slurry is coated in copper current collector up to about 50 μm of thickness using scraper, is done at about 80 DEG C in an oven It dry about 2 hours, is then further dried at about 120 DEG C about 2 hours in a vacuum, thus manufactures cathode.

Use the cathode, the lithium metal as to electrode, polypropylene separator (Celgard3510) and is dissolved in 3:7 Volume ratio EC (ethylene carbonate) and DEC (diethyl carbonate) in the mixed solvent 1.3M LiPF₆Electrolyte manufacture is hard Coin half-cell battery (CR-2032 standard).

Embodiment 2: the manufacture of cathode and coin half-cell battery

Coin half-cell battery is manufactured in the same manner as in example 1, in addition to use preparation embodiment 2 includes poly- (lithium degree of substitution: 1.0) replace preparation embodiment 1 includes poly- { (isobutene-to the composition of (isobutene-alt- maleic acid lithium salts) Alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) composition (lithium degree of substitution: 0.8) as binder it Outside.

Embodiment 3: the manufacture of cathode and coin half-cell battery

Using 4.4g as graphite (M1) powder (being available from Carbonics Co.) (D50=1 μm) of negative electrode active material and 12g as binder preparation embodiment 3 include the poly- { (Malaysia isobutene-alt- (isobutene-alt- maleic anhydride)-co- Sour lithium salts) } composition (lithium degree of substitution: 0.5) mixed with the weight ratio of 88:12 to prepare slurry.

The slurry is coated in copper current collector up to about 50 μm of thickness using scraper, is done at about 80 DEG C in an oven It dry about 2 hours, is then further dried at about 120 DEG C about 2 hours in a vacuum, thus manufactures cathode.

Use the cathode, the lithium metal as to electrode, polypropylene separator (Celgard3510) and is dissolved in 3:7 Volume ratio EC (ethylene carbonate) and DEC (diethyl carbonate) in the mixed solvent 1.3M LiPF₆Electrolyte manufacture is hard Coin half-cell battery (CR-2032 standard).

Embodiment 4: the manufacture of cathode and coin half-cell battery

Coin half-cell battery is manufactured in mode in the same manner as in Example 3, the packet in addition to using 12g preparation embodiment 4 Composition (lithium degree of substitution: 0.6) containing poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } What it is instead of 12g preparation embodiment 3 includes poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (lithium degree of substitution: 0.5) as except binder.

Embodiment 5: the manufacture of cathode and coin half-cell battery

Coin half-cell battery is manufactured in mode in the same manner as in Example 3, the packet in addition to using 12g preparation embodiment 5 Composition (lithium degree of substitution: 0.7) containing poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } What it is instead of 12g preparation embodiment 3 includes poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (lithium degree of substitution: 0.5) as except binder.

Embodiment 6: the manufacture of cathode and coin half-cell battery

Coin half-cell battery is manufactured in mode in the same manner as in Example 3, the packet in addition to using 12g preparation embodiment 1 Composition (lithium degree of substitution: 0.8) containing poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } What it is instead of 12g preparation embodiment 3 includes poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Composition (lithium degree of substitution: 0.5) as except binder.

Embodiment 7: the manufacture of cathode and coin half-cell battery

Coin half-cell battery is manufactured in mode in the same manner as in Example 3, the packet in addition to using 12g preparation embodiment 2 (lithium degree of substitution: 1.0) replace 12g preparation embodiment 3 includes poly- to composition containing poly- (isobutene-alt- maleic acid lithium salts) Composition (the lithium degree of substitution: 0.5) conduct of { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } Except binder.

Embodiment 8: the manufacture of cathode and coin half-cell battery

It is real as the preparation of binder using 4g as silicon/carbon nanotube (" CNT ") compound of negative electrode active material and 20g Apply composition (the lithium degree of substitution: 1.0) with the weight of 80:20 for poly- (isobutene-alt- maleic acid lithium salts) of example 2 replaced comprising lithium Amount ratio is mixed to prepare slurry.

Silicon/carbon nanotube (" CNT ") compound is prepared by following procedure.

The Si with 150nm partial size is mixed with carbon nanotube (" CNT ") with the mixed weight ratio of 3:7 first, is then made Gains undergo high-energy ball milling to obtain the silicon/carbon nanotube (" CNT ") compound.

The slurry is coated in copper current collector up to about 50 μm of thickness using scraper, is done at about 80 DEG C in an oven It dry about 2 hours, is then further dried at about 120 DEG C about 2 hours in a vacuum, thus manufactures cathode.

Use the cathode, the lithium metal as to electrode, polypropylene separator (Celgard3510) and be dissolved in 2:6: The EC (ethylene carbonate) of 2 volume ratio, the in the mixed solvent of DEC (diethyl carbonate) and FEC (fluoroethylene carbonate) 1.3M LiPF₆Electrolyte manufactures coin half-cell battery (CR-2032 standard).

Embodiment 9: the manufacture of cathode and coin half-cell battery

Using 3.5g as the Mn oxide (MnOx, 0 < x≤2) of negative electrode active material, 0.75g carbonaceous conductive agent (Super-P, Be available from Timcal Inc.) and 15g preparation embodiment 1 comprising poly- { (isobutene-alt- maleic anhydride)-co- (isobutene- Alt- maleic acid lithium salts) } composition (lithium degree of substitution: 0.8) mixed with the weight ratio of 70:15:15 to prepare slurry.

The slurry is coated in copper current collector up to about 50 μm of thickness using scraper, is done at about 80 DEG C in an oven It dry about 2 hours, is then further dried at about 120 DEG C about 2 hours in a vacuum, thus manufactures cathode.

Use the cathode, the lithium metal as to electrode, polypropylene separator (Celgard3510) and be dissolved in 2:6: The EC (ethylene carbonate) of 2 volume ratio, the in the mixed solvent of DEC (diethyl carbonate) and FEC (fluoroethylene carbonate) 1.3M LiPF₆Electrolyte manufactures coin half-cell battery (CR-2032 standard).

Embodiment 10: the manufacture of cathode and coin half-cell battery

Coin half-cell battery is manufactured in mode in the same manner as in Example 9, the packet in addition to using 15g preparation embodiment 2 Composition (lithium degree of substitution: 1.0) instead of 12g preparation embodiment 1 containing poly- (isobutene-alt- maleic acid lithium salts) that lithium replaces Comprising poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } composition (lithium degree of substitution: 0.8) as except binder.

Embodiment 11: the manufacture of cathode and coin half-cell battery

Make 4.4g as graphite (M1) (D50=1 μm) powder (being available from Carbonics) and 6g of negative electrode active material For binder preparation embodiment 7 include poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid ammonium Salt) } polymer composition mix to prepare slurry.Solid component, that is, negative electrode active material in the slurry with as bonding The Mixing ratio by weight of poly- { (isobutene-alt- maleic anhydride)-co- (Malaysia the isobutene-alt- acid ammonium salt) } of agent is about 88: 12。

The slurry is coated in Cu collector up to about 50 μm of thickness using scraper.Then, by gains in baking oven In dry about 2 hours at about 80 DEG C, dry 2 hours again at about 120 DEG C in a vacuum then to manufacture negative plate.

Use the negative plate, as to electrode lithium metal, as partition polypropylene separator (Celgard3510), And by dissolving 1.3M in the in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 3:7) LiPF₆The electrolyte solution of acquisition manufactures CR-2032 standard coinage half-cell battery.

Embodiment 12: the manufacture of cathode and coin half-cell battery

Using 4.4g as graphite (M1) (D50=about 1 μm) powder (being available from Carbonics) and 6g of negative electrode active material Preparation embodiment 8 as binder includes poly- { (ethylene-alt- maleic anhydride)-co- (ethylene-alt- maleic acid lithium salts) } Polymer composition (with 0.5 lithium degree of substitution) mixing to prepare slurry.Solid component, that is, cathode in the slurry is living Property substance and poly- { (ethylene-alt- maleic anhydride)-co- (ethylene-alt- maleic acid lithium salts) } as binder weight it is mixed Composition and division in a proportion is about 88:12.

The slurry is coated in Cu collector up to about 50 μm of thickness using scraper.Then, by gains in baking oven In dry about 2 hours at about 80 DEG C, dry 2 hours again at about 120 DEG C in a vacuum then to manufacture negative plate.

Use the negative plate, as to electrode lithium metal, as partition polypropylene separator (Celgard3510), And by dissolving 1.3M in the in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 3:7) LiPF₆The electrolyte solution of acquisition manufactures CR-2032 standard coinage half-cell battery.

Embodiment 13: the manufacture of cathode and coin half-cell battery

Using 4.5g as graphite (SFG6) (D90=about 6.5 μm) powder (being available from TIMCAL Co.) of negative electrode active material With 5g as binder preparation embodiment 7 include the poly- { (Malaysia isobutene-alt- (isobutene-alt- maleic anhydride)-co- Acid ammonium salt) } polymer composition mix to prepare slurry.Solid component, that is, negative electrode active material and conduct in the slurry The Mixing ratio by weight of poly- { (isobutene-alt- maleic anhydride)-co- (Malaysia the isobutene-alt- acid ammonium salt) } of binder is about 90:10。

The slurry is coated in Cu collector up to about 50 μm of thickness using scraper.Then, by gains in baking oven In dry about 2 hours at about 80 DEG C, dry 2 hours again at about 120 DEG C in a vacuum then to manufacture negative plate.

Use the negative plate, as to electrode lithium metal, as partition polypropylene separator (Celgard3510), And by dissolving 1.3M in the in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 3:7) LiPF₆The electrolyte solution of acquisition manufactures CR-2032 standard coinage half-cell battery.

Embodiment 14: the manufacture of cathode and coin half-cell battery

Using 4.5g as graphite (SFG6) (D90=about 6.5 μm) powder (being available from TIMCAL Co.) of negative electrode active material With 5g as binder preparation embodiment 8 include poly- { (ethylene-alt- maleic anhydride)-co- (ethylene-alt- maleic acid lithium Salt) } polymer composition (with 0.5 lithium degree of substitution) mixing to prepare slurry.Solid component in the slurry is i.e. negative The weight of pole active material and poly- { (ethylene-alt- maleic anhydride)-co- (ethylene-alt- maleic acid lithium salts) } as binder Measuring mixing ratio is about 90:10.

The slurry is coated in Cu collector up to about 50 μm of thickness using scraper.Then, by gains in baking oven In dry about 2 hours at about 80 DEG C, dry 2 hours again at about 120 DEG C in a vacuum then to manufacture negative plate.

Use the negative plate, as to electrode lithium metal, as partition polypropylene separator (Celgard3510), And by dissolving 1.3M in the in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 3:7) LiPF₆The electrolyte solution of acquisition manufactures CR-2032 standard coinage half-cell battery.

Comparative example 1: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in the same manner as in example 1, in addition to using 8.33g6 weight hundred The Kynoar binder solution (solvent: N-Methyl pyrrolidone (" NMP ")) of score (" weight % ") replaces preparation embodiment 1 comprising poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } composition (lithium degree of substitution: 0.8) as except binder.

Comparative example 2: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in the same way as in comparative example 1, in addition to using 8.33g6 weight %'s Poly- (isobutene-alt- maleic anhydride) (the mole mixture ratio 1:1 of isobutene and maleic anhydride；Solvent: N-Methyl pyrrolidone ("NMP")；The weight average molecular weight of about 300,000-350,000) binder solution replace Kynoar binder solution Except.

Comparative example 3: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in mode in the same manner as in Example 3, in addition to using gathering for 10g6 weight % What vinylidene binder solution (N-Methyl pyrrolidone (" NMP ") solvent) replaced preparation embodiment 3 includes poly- { (isobutene- Alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) composition (lithium degree of substitution: except 0.5).

Comparative example 4: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in mode in the same manner as in Example 3, in addition to using gathering for 10g6 weight % (isobutene-alt- maleic anhydride) binder solution (1:1 mole mixture ratio of isobutene and maleic anhydride；About 300,000- 350,000 weight average molecular weight；With N-Methyl pyrrolidone (" NMP ") solvent) it replaces except Kynoar binder solution.

Comparative example 5: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in mode in the same manner as in Example 8, in addition to using gathering for 20g5 weight % What amide imide binder solution (N-Methyl pyrrolidone (" NMP ") solvent) replaced preparation embodiment 2 includes poly- (isobutyl Alkene-alt- maleic acid lithium salts) composition (lithium degree of substitution: except 1.0).

Comparative example 6: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in a manner of identical with comparative example 5, in addition to using 16.7g6 weight %'s Poly- (isobutene-alt- maleic anhydride) (" PIBMA ") binder solution (the 1:1 mole mixture ratio of isobutene and maleic anhydride；About The weight average molecular weight of 300,000-350,000；With N-Methyl pyrrolidone (" NMP ") solvent) replace polyamidoimide to bond Except agent solution.

Comparative example 7: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in mode in the same manner as in Example 9, in addition to using gathering for 15g5 weight % What amide imide (" PAI ") binder solution (N-Methyl pyrrolidone (" NMP ") solvent) replaced preparation embodiment 1 includes poly- Composition (the lithium degree of substitution: except 0.8) of { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) }.

Comparative example 8: the manufacture of cathode and coin half-cell battery

Cathode and coin half-cell battery are manufactured in a manner of identical with comparative example 7, in addition to using 12.5g6 weight %'s Poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } (lithium substitution comprising preparing embodiment 1 Degree: 0.8) binder solution (solvent: N-Methyl pyrrolidone (NMP)) replaces except polyamidoimide binder solution.

Evaluate embodiment 1:¹H-NMR analysis

Pass through¹H- nuclear magnetic resonance (" NMR ") spectrometry passes through as described below sample preparation analysis preparation embodiment 1,3-6 Composition comprising poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } and preparation embodiment 2 The composition comprising poly- (isobutene-alt- maleic acid lithium salts).As a result it is shown in Fig. 2-6.

For H NMR spectroscopy method, by each inherent filtration of composition that will prepare embodiment 1-6, then remove cannot be molten part And it is extracted from the composition poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } and poly- (different Butylene-alt- maleic acid lithium salts).

The structure determination of (isobutene-alt- maleic acid lithium salts) unit is with following formula:

In above formula,

Y₇And Y₈At least one be lithium, and Y₇And Y₈Remaining be hydrogen atom, and n as the degree of polymerization is about 1,945- 2,270.Although not showing the mixing ratio of each repetitive unit, the molar fraction of isobutylene repeat units is about 0.5, and maleic acid The molar fraction of acid anhydride repetitive unit is about 0.5.

In above formula, the proton in different magnetic environments is indicated with a, b, c and d to be distinguished from each other.

Fig. 2-4 is the poly- (isobutene-alt- maleic acid for showing the lithium substitution corresponding to the proton peak of proton a, b, c and d Acid anhydride) H NMR spectroscopy.In Fig. 2-4, a, b, c and d are respectively the proton peak for corresponding to proton a, b, c and d.

By prepare embodiment 1,3-6 include poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid Lithium salts) } composition and preparation embodiment 2 each inherent filtration of composition comprising poly- (isobutene-alt- maleic acid lithium salts), so Remove water-insoluble part afterwards to obtain the solid component of filtering.It is poly- { (different to obtain that water is removed from the solid component of the filtering Butylene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } and it is poly- (isobutene-alt- maleic acid lithium salts).

By poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } and poly- (isobutyl Alkene-alt- maleic acid lithium salts) respectively it is dissolved in D₂It is used in O with preparation¹The sample of H-NMR spectrometry, it is described¹H-NMR spectrometry uses H NMR spectroscopy instrument (300MHz, DPX300 are available from Bruker Co.) carries out.

Referring to Fig.1, maleic anhydride repeat units-COOH group in hydrogen replaced by lithium in the case where, proton a or matter The chemical shift of sub- b depends on proton a or proton b and is integrated to the position of main polymer chain and occurs.Lithium degree of substitution is higher, proton The chemical shift of a is directed downwardly toward more from 2.75ppm or smaller, and the chemical shift of proton b is led downwards from 2.4ppm or smaller To more.

The enlarged drawing in the center that Fig. 3 and 4 is the peak a and b in the H NMR spectroscopy.

Clearer to be referring to Fig. 3 and 4, the chemical shift of peak a and peak b depend on the degree of substitution of lithium ion and change.

Figures 5 and 6 illustrate relative in poly- (isobutene-alt- maleic anhydride) (" PIBMA ") and poly- { (isobutene-alt- Maleic anhydride) in-co- (isobutene-alt- maleic acid lithium salts) and poly- (isobutene-alt- maleic acid lithium salts) (" Li-PIBMA ") Lithium degree of substitution preparation embodiment 1,3-6 include poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- horse Come sour lithium salts) composition and preparation embodiment 2 the composition comprising poly- (isobutene-alt- maleic acid lithium salts) in peak a With the chemical shift of peak b.

Evaluate embodiment 2:ICP-AES analysis

From preparation embodiment 1,3-6 include poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid Lithium salts) } composition and preparation embodiment 2 the composition comprising poly- (isobutene-alt- maleic acid lithium salts) respectively remove water To obtain poly- { (isobutene-alt- maleic anhydride)-co- (isobutene-alt- maleic acid lithium salts) } and poly- (isobutyl of solid form Alkene-alt- maleic acid lithium salts), then pass through inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis.As a result It is shown in the following table 1.Shimadzu ICP8100 analyzer is used in ICP-AES.

Table 1

Embodiment	Binder	Li content
			Prepare embodiment 1	Li-0.8-PIBMA	4.30 weight %
Prepare embodiment 2	Li-1.0-PIBMA	5.50 weight %
			Prepare embodiment 3	Li-0.5-PIBMA	3.00 weight %
Prepare embodiment 4	Li-0.6-PIBMA	3.10 weight %
			Prepare embodiment 5	Li-0.7-PIBMA	3.80 weight %

Evaluate embodiment 3: the evaluation of charge-discharge characteristics

Following evaluation charge-discharge characteristics.Starting efficiency is calculated using following Equation 1.

Equation 1

Starting efficiency (%)=(discharge capacity/charging capacity) × 100

1) use as the graphite of negative electrode active material (SFG6)

By the coin half-cell battery of Examples 1 and 2 and comparative example 1 and 2 respectively with 30 milliamperes of (" mA ")/1g active matters The constant current charging of matter to 0.001 volt (" V ") (relative to Li) voltage, then with constant voltage charging to 15 milliamperes/gram (" mA/g "), is discharged to the voltage of 1.0V (relative to Li) then with identical constant current.

The first time cyclic discharge capacity of the coin half-cell battery of Examples 1 and 2 and comparative example 1 and 2 and initial effect Rate is shown in the following table 2.

Table 2

Embodiment	Binder	Capacity (mAh/g)	Starting efficiency (%)
				Embodiment 1	Li-0.8-PIBMA	333	84.3
Embodiment 2	Li-1.0-PIBMA	333	83.8
				Comparative example 1	PVDF	329	78.2
Comparative example 2	PIBMA	335	80.9

Referring to table 2, find due to the side reaction between repressed negative electrode active material and electrolyte solution, embodiment 1 There is improved starting efficiency compared with the coin half-cell battery of comparative example 1 and 2 with 2 coin half-cell battery.

2) use as the graphite of negative electrode active material (M1)

Implementation is evaluated in such a way that those of coin half-cell battery with Examples 1 and 2 and comparative example 1 and 2 is identical The charge-discharge characteristics of example 3-7 and the coin half-cell battery of comparative example 3 and 4.

The first time cyclic discharge capacity and starting efficiency of embodiment 3-7 and the coin half-cell battery of comparative example 3 and 4 It is shown in the following table 3.

Table 3

Embodiment	Binder	Capacity (mAh/g)	Starting efficiency (%)
				Comparative example 3	PVDF	316	67.7
Comparative example 4	PIBMA	327	70.5
				Embodiment 3	Li-0.5-PIBMA	317	78.0
Embodiment 4	Li-0.6-PIBMA	318	76.0
				Embodiment 5	Li-0.7-PIBMA	324	79.1
Embodiment 6	Li-0.8-PIBMA	325	77.6
				Embodiment 7	Li-1.0-PIBMA	330	77.4

Referring to table 3, find due to the side reaction between repressed negative electrode active material and electrolyte solution, embodiment 3- 7 coin half-cell battery has improved starting efficiency compared with the coin half-cell battery of comparative example 3 and 4.

3) use as the Si/CNT compound of negative electrode active material

Implementation is evaluated in such a way that those of coin half-cell battery with Examples 1 and 2 and comparative example 1 and 2 is identical The charge-discharge characteristics of the coin half-cell battery of example 8 and comparative example 5 and 6.As a result it is shown in the following table 4.

The first time cyclic discharge capacity and starting efficiency of the coin half-cell battery of embodiment 8 and comparative example 5 and 6 show In table 4.

Table 4

Embodiment	Binder	Capacity (mAh/g)	Starting efficiency (%)
				Comparative example 5	PAI	1,170	61.8
Comparative example 6	PIBMA	1,030	62.2
				Embodiment 8	Li-1.0-PIBMA	1,180	72.2%

4) as the MnO of negative electrode active material_XUse

Implementation is evaluated in such a way that those of coin half-cell battery with Examples 1 and 2 and comparative example 1 and 2 is identical The charge-discharge characteristics of the coin half-cell battery of example 9 and 10 and comparative example 7 and 8.As a result it is shown in the following table 5.

The first time cyclic discharge capacity of the coin half-cell battery of embodiment 9 and 10 and comparative example 7 and 8 and initial effect Rate is shown in Table 5.

Table 5

Embodiment	Binder	Capacity (mAh/g)	Starting efficiency (%)
				Comparative example 7	PAI	973	71.1
Comparative example 8	PIBMA	637	51.2
				Embodiment 9	Li-0.8-PIBMA	914	75.9
Embodiment 10	Li-1.0-PIBMA	925	76.9

Referring to table 5, find due to the side reaction between repressed negative electrode active material and electrolyte, embodiment 9 and 10 Coin half-cell battery compared with the coin half-cell battery of comparative example 7 and 8 have improved starting efficiency.

Evaluate embodiment 4: the evaluation of charge-discharge characteristics

Following evaluation charge-discharge characteristics.Starting efficiency is calculated using following Equation 1.

Equation 1

Starting efficiency (%)=(discharge capacity/charging capacity) × 100

1) the coin half-cell battery of embodiment 11-12 and comparative example 1

By the coin half-cell battery of embodiment 11 and 12 and comparative example 1 respectively with the constant of 30mA/1g active material Electric current charges to the voltage of 0.001V (relative to Li), then with identical constant voltage charging to about 15mA/g, then with phase Same constant current is discharged to the voltage of 1.0V (relative to lithium).The coin half-cell electricity of embodiment 11 and 12 and comparative example 1 The first time cyclic discharge capacity in pond is shown in Table 6.

Table 6

Embodiment	Binder	Reversible capacity (mAh/g)	Starting efficiency (%)
				Comparative example 1	PVDF	316	67.7
Embodiment 11	NH4-PIBMA	354	73.2
				Embodiment 12	Li-0.5-PEMA	312	80.0

It referring to table 6, finds compared with the coin half-cell battery of comparative example 1, the coin half-cell electricity of embodiment 11 and 12 Pond has improved starting efficiency.

2) the coin half-cell battery of embodiment 13-14 and comparative example 2

By the coin half-cell battery of embodiment 13 and 14 and comparative example 2 respectively with the constant of 30mA/1g active material Electric current charges to the voltage of about 0.001V (relative to Li), then with identical constant voltage charging to 15mA/g, then with phase Same constant current is discharged to the voltage of 1.0V (relative to lithium).The coin half-cell electricity of embodiment 13 and 14 and comparative example 2 The first time cyclic discharge capacity in pond is shown in Table 7.

Table 7

Embodiment	Binder	Reversible capacity (mAh/g)	Starting efficiency (%)
				Comparative example 2	PVDF	329	78.2
Embodiment 13	NH4-PIBMA	360	78.6
				Embodiment 14	Li-0.5-PEMA	345	82.5

It referring to table 7, finds compared with the coin half-cell battery of comparative example 2, the coin half-cell electricity of embodiment 13 and 14 Pond has improved starting efficiency and improved reversible capacity.

As described above, the one or more for the embodiment of above conceived according to the present invention, including indicated by equation 1 above The polymer of one repetitive unit can be formed organosilicon prepolymer solid electrolyte interface (" PRE-SEI ") on the surface of electrode active material Thus film is pressed down with covering the defect of electrode active material and directly contacting between blocking electrode active material and electrolyte solution Side reaction processed and the starting efficiency for therefore improving the lithium battery.

It should be understood that illustrative embodiments described in it should consider in the sense of description only and be not used in the mesh of limitation 's.The description of features or aspect in each embodiment should be typically considered to can be used for other classes in other embodiment As features or aspect.

Claims (12)

1. purposes of the polymer for the binders for electrodes of lithium battery, wherein the polymer is indicated by formula 8 or 8z:

Formula 8

Formula 8z

Wherein, in formula 8 and 8z, i) Y₇And Y₈It both is lithium or ii) Y₇And Y₈One of be lithium, and remaining be hydrogen atom,

A is the molar fraction of 0 or 0.01-0.99, and b is the molar fraction and a+b=1 of 1 or 0.01-0.99,

M and n is respectively the molar fraction and m+n=1 of 0.01-0.99.

2. the purposes of claim 1, wherein in formula 8 and 8z, a 0, b 1, and Y₇And Y₈It both is lithium.

3. the purposes of claim 1, wherein the polymer is 0.2-1.0 by the degree of substitution of alkali metal or ammonium.

4. the purposes of claim 1, wherein the polymer exists¹At -2.75 million points of 2.65 parts per million in H nuclear magnetic resoance spectrum Maleic anhydride and the horse in auto polymerization object chain are showed in the chemical shift range of -2.4 parts per million of rate and 2.2 parts per million Carry out sour at least one two proton peak.

5. the purposes of claim 1, wherein the polymer has 50,000-500,000 weight average molecular weight.

6. the purposes of claim 1, wherein the lithium content in the polymer is 2 weight %-15 weight %.

7. the purposes of claim 1, wherein the polymer is reaction product below:

(i) alkali of alkali metal containing or ammonium, and

(ii) polymer A comprising by formula 4c or formula 4d the first repetitive unit indicated and be selected from divalent aliphatic organic group Second repetitive unit of repetitive unit and divalent alicyclic organic group repetitive unit:

Formula 4c

Wherein, in formula 4c,

R₇And R₈It is each independently hydrogen atom；

Formula 4d

Wherein, in formula 4d,

R₇And R₈It is each independently hydrogen atom；With

The molar fraction of first repetitive unit is 0.01-0.99,

Molar fraction with second repetitive unit is 0.01-0.99,

Wherein second repetitive unit is indicated by formula 5:

Formula 5

Wherein, in formula 5,

R₉And R₁₁For C1 alkyl, and R₁₀And R₁₂For hydrogen atom；With

The polymer has the degree of polymerization of 100-50,000.

8. the purposes of claim 7, wherein the alkali of the alkali metal containing or ammonium be selected from lithium hydroxide and ammonium hydroxide extremely Few one kind.

9. the purposes of claim 7, wherein the reaction product be mixture 20 DEG C -100 DEG C at a temperature of reaction product, The mixture includes: the polymer A, the alkali and water of the alkali metal containing or ammonium.

10. being used for the electrode of lithium battery, comprising:

If the polymer limited in claim any one of 1-9 is as binder；With

Electrode active material.

11. the electrode of claim 10, wherein the electrode active material based on 100 parts by weight, the amount of the polymer is 1 - 30 parts by weight of parts by weight.

12. including the lithium battery of the electrode of claim 10 or 11.