CN109851703A - Vinylidene fluoride analog copolymer and its preparation method and application suitable for binder - Google Patents
Vinylidene fluoride analog copolymer and its preparation method and application suitable for binder Download PDFInfo
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Abstract
The present invention relates to field of lithium, and in particular to the vinylidene fluoride analog copolymer and its preparation method and application suitable for binder.The vinylidene fluoride analog copolymer contains structural unit shown in structural unit shown in structural unit shown in following formula (1), formula (2) and formula (3).Novel vinylidene fluoride analog copolymer provided by the invention can dissolve well in huge polarity and nonpolar solvent；There is better tolerance to strong alkali environment simultaneously；In addition it can reduce influence of the binder for Ion transfer in pole piece；When to be used as binder in lithium battery, enable to resulting lithium battery that there is higher specific capacity and cycle performance.
Description
Technical field
The present invention relates to field of lithium, and in particular to suitable for the vinylidene fluoride analog copolymer of binder and its preparation
Methods and applications.
Background technique
PVDF class binder is the binder of lithium ion battery preparation field routine, and usually it includes pure poly- inclined difluoro second
Alkene, polyvinylidene fluoride polymer-modified are copolymerized the polymer formed by vinylidene fluoride and hexafluoropropene.And these
Formant is vinylidene fluoride units in the structure of macromolecular chain in binder.However, existing PVDF class binder exists
Following defect:
(1) cost of material of PVDF class binder is high；
(2) PVDF class binder may not apply to strong basicity environment.It is easy defluorinate in the solution of pH > 10, while can lead
Cause adhesive failure.This phenomenon can have embodiment in the preparation of tertiary cathode material slurry.
(3) PVDF class binder can only dissolve in the organic solvent of the limited kinds such as NMP, DMF, DMSO, this limits it
The improvement of application and corresponding technique during specific experiment.
Summary of the invention
The purpose of the present invention is to provide a kind of novel vinylidene fluoride analog copolymers and its system suitable for binder
Preparation Method and application, the vinylidene fluoride analog copolymer can be molten well in huge polarity and nonpolar solvent
Solution；There is better tolerance to strong alkali environment simultaneously；In addition it can reduce influence of the binder for Ion transfer in pole piece.
To achieve the goals above, one aspect of the present invention provides a kind of vinylidene fluoride class copolymerization suitable for binder
Object, the copolymer contain structure list shown in structural unit shown in structural unit shown in following formula (1), formula (2) and formula (3)
Member；
Formula (1)Formula (2)Formula (3)
Wherein, Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-(CH2CH2O)m-、-(OCH2CH2)m-、-
(CO)-O- or-O- (CO)-, k are each independently the integer of 1-5, and m is each independently the integer of 1-20；
RfFor-ChF2h+1, h is the integer of 0-10；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i 0-
10 integer；
Cationic Y+For H+、Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Al3+, cation shown in formula (4),
Cation shown in formula (5), cation, formula (9) shown in cation, formula (8) shown in cation, formula (7) shown in formula (6)
Shown in any one in cation shown in cation and formula (10):
Formula (4)Formula (5)Formula (6)Formula (7)Formula (8)Formula (9)Formula (10)Wherein, R1、R2、R3And R4Respectively
From alkyl or-(CH independently selected from C1-C102CH2O)j-CH3, j is each independently the integer of 1-10.
Second aspect of the present invention provides a kind of preparation method of vinylidene fluoride analog copolymer, this method comprises: in freedom
In the presence of base initiator, in organic solvent, by monomer shown in monomer shown in formula (1-a), formula (2-a) and formula (3-a) institute
The monomer shown carries out copolyreaction, wherein
Formula (1-a)Formula (2-a) CF2=CH2, formula (3-a)
Wherein, Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-(CH2CH2O)m-、-(OCH2CH2)m-、-
(CO)-O- or-O- (CO)-, k are each independently the integer of 1-5, and m is each independently the integer of 1-20；
RfFor-ChF2h+1, h is the integer of 0-10；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i 0-
10 integer；
Cationic Y+For H+、Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Al3+, cation shown in formula (4),
Cation shown in formula (5), cation, formula (9) shown in cation, formula (8) shown in cation, formula (7) shown in formula (6)
Shown in any one in cation shown in cation and formula (10):
Formula (4)Formula (5)Formula (6)
Formula (7)Formula (8)Formula (9)Formula (10)
Wherein, R1、R2、R3And R4It is each independently selected from the alkyl or-(CH of C1-C102CH2O)j-CH3, j is each independently
For the integer of 1-10.
Third aspect present invention provides the vinylidene fluoride analog copolymer as made from the method for above-mentioned second aspect.
Fourth aspect present invention provides above-mentioned vinylidene fluoride analog copolymer answering as binder in lithium ion battery
With.
Fifth aspect present invention provides a kind of battery electrode, and the electrode includes: that electrode current collecting body and its surface are adhered to
Electrode material layer, the electrode material layer contain electrode active material and binder, and the binder contains above-mentioned inclined difluoro second
Vinyl copolymer.
Sixth aspect present invention provides the preparation method of battery electrode described in the 5th aspect, this method comprises:
(1) electrode slurry containing electrode active material, optional conductive agent and binder is provided；
(2) electrode slurry of step (1) is coated on electrode current collecting body, and dry, to be formed on electrode current collecting body
Electrode material layer.
Seventh aspect present invention provides a kind of lithium battery, which includes: anode, cathode, battery diaphragm and electrolyte,
In, the anode and/or cathode are above-mentioned battery electrode.
Novel vinylidene fluoride analog copolymer provided by the invention, can be in huge polarity and nonpolar solvent
It can dissolve well；There is better tolerance to strong alkali environment simultaneously；In addition can reduce in pole piece binder for from
The influence of son migration；When to be used as binder in lithium battery, enable to resulting lithium battery that there is higher specific capacity
And cycle performance.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of vinylidene fluoride analog copolymer suitable for binder, which contains following formula
(1) structural unit shown in structural unit shown in structural unit, formula shown in (2) and formula (3)；
Formula (1)Formula (2)Formula (3)
Wherein, Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-(CH2CH2O)m-、-(OCH2CH2)m-、-
(CO)-O- or-O- (CO)-, k are each independently the integer of 1-5, and m is each independently the integer of 1-20；
RfFor-ChF2h+1, h is the integer of 0-10；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i 0-
10 integer；
Cationic Y+For H+、Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Al3+, cation shown in formula (4),
Cation shown in formula (5), cation, formula (9) shown in cation, formula (8) shown in cation, formula (7) shown in formula (6)
Shown in any one in cation shown in cation and formula (10):
Formula (4)Formula (5)Formula (6)Formula (7)FormulaFormula (9)Formula (10)Wherein, R1、R2、R3And R4Respectively
From alkyl or-(CH independently selected from C1-C102CH2O)j-CH3, j is each independently the integer of 1-10.
In accordance with the present invention it is preferred that Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-(CH2CH2O)m-、-
(OCH2CH2)m,-(CO)-O- or-O- (CO)-, k be each independently 1,2 or 3, and m is each independently the integer of 1-10；Rf
For-ChF2h+1, h is the integer of 0-5；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i is the integer of 0-5；R1、
R2、R3And R4It is each independently selected from the alkyl or-(CH of C1-C52CH2O)j-CH3, j is each independently the integer of 1-5.
It is highly preferred that Z is each independently selected from singly-bound ,-CH2-、-CH2-CH2-、-CF2-、-CF2-CF2-、-CH2CH2O-、-
OCH2CH2,-(CO)-O- or-O- (CO)-；RfFor-F ,-CF3Or-CF2CF3, Rf1、Rf2And Rf3Be each independently-H ,-
CH3、-CH2CH3、-F、-CF3Or-CF2CF3；R1、R2、R3And R4Be each independently selected from methyl, ethyl, n-propyl, isopropyl,
Normal-butyl ,-CH2CH2O-CH3Or-(CH2CH2O)2-CH3。
Wherein, Z is that singly-bound refers to that Z is only connecting key, and the group at both ends is directly connected to.
According to the present invention, structural unit shown in formula (1) is preferably selected from one of following structural unit or a variety of:
Formula (1-1): in formula (1), Z is singly-bound, RfFor F, Rf1And Rf2For F, Rf3For H, Y+For Li+；
Formula (1-2): in formula (1), Z is singly-bound, RfFor F, Rf1And Rf2For F, Rf3For H, Y+For cation shown in formula (10),
And in formula (10), R1For ethyl, R2For methyl.
It should be understood that for cationic Y+Transformation can be by unused cation Y+Salt and existing offer on
The monomer for stating structural unit carries out ion exchange, can be obtained other cationic Y+Formula (1) shown in structural unit.
According to the present invention, it is tied shown in structural unit and formula (3) shown in structural unit, formula (2) shown in the formula (1)
The ratio of structure unit can change in a wider range, it is preferable that structural unit shown in the formula (1) is tied shown in formula (2)
The molar ratio of structural unit shown in structure unit and formula (3) is 0.001-999:1:0.001-9, preferably 0.01-100:1:
0.005-5, more preferably 0.1-9:1:0.01-1 are still more preferably 0.5-5:1:0.01-0.5, preferably 0.5-2:1:
0.01-0.1。
According to the present invention, in order to obtain the more excellent binder of performance, it is preferable that the weight average molecular weight of the copolymer
It is 50,000-2,000,000g/mol, preferably 100,000-1,000,000g/mol, more preferably 200,000-800,
000g/mol is still more preferably 250,000-500,000g/mol.Wherein, the molecule of the vinylidene fluoride analog copolymer
Measuring profile exponent is preferably 1.1-2, preferably 1.1-1.6.
According to the present invention, the vinylidene fluoride analog copolymer of the invention can be random copolymer, alternate copolymer or
Structural unit shown in block copolymer, preferably random copolymer, the especially structural unit as shown in formula (1), formula (2) and
The random copolymer of the composition of structural unit shown in formula (3).
Second aspect of the present invention provides a kind of preparation method of vinylidene fluoride analog copolymer, this method comprises: in freedom
In the presence of base initiator, in organic solvent, by monomer shown in monomer shown in formula (1-a), formula (2-a) and formula (3-a) institute
The monomer shown carries out copolyreaction, wherein
Formula (1-a)Formula (2-a) CF2=CH2, formula (3-a)
Wherein, Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-(CH2CH2O)m-、-(OCH2CH2)m-、-
(CO)-O- or-O- (CO)-, k are each independently the integer of 1-5, and m is each independently the integer of 1-20；
RfFor-ChF2h+1, h is the integer of 0-10；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i 0-
10 integer；
Cationic Y+For H+、Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Al3+, cation shown in formula (4),
Cation shown in formula (5), cation, formula (9) shown in cation, formula (8) shown in cation, formula (7) shown in formula (6)
Shown in any one in cation shown in cation and formula (10):
Formula (4)Formula (5)Formula (6)Formula (7)Formula (8)Formula (9)Formula (10)Wherein, R1、R2、R3And R4Respectively
From alkyl or-(CH independently selected from C1-C102CH2O)j-CH3, j is each independently the integer of 1-10.
According to the present invention, group involved in structure above is as described above, and details are not described herein the present invention.
Wherein, monomer shown in formula (1-a) can the structural unit according to shown in Chinese style above (1) properly selected.
Preferably, monomer shown in formula (1-a) is selected from one of following monomer or a variety of:
Formula (1-a-1): in formula (1-a), Z is singly-bound, RfFor F, Rf1And Rf2For F, Rf3For H, Y+For Li+；
Formula (1-a-2): in formula (1-a), Z is singly-bound, RfFor F, Rf1And Rf2For F, Rf3For H, Y+For sun shown in formula (10)
Ion, and in formula (10), R1For ethyl, R2For methyl.
According to the present invention, the preparation of monomer shown in formula (1-a) can specifically be designed according to its structure, specifically may be used
With reference to the method in subsequent embodiment, there is no particular limitation to this by the present invention.
According to the present invention, the use of monomer shown in monomer and formula (3-a) shown in monomer, formula (2-a) shown in formula (1-a)
Amount proportion can be matched according to the structural unit of required vinylidene fluoride analog copolymer and molecular weight is determined, wherein excellent
The molar ratio of selection of land, the dosage of monomer shown in monomer and formula (3-a) shown in monomer, formula (2-a) shown in formula (1-a) is
0.001-999:1:0.001-9, preferably 0.01-100:1:0.005-5, more preferably 0.1-9:1:0.01-1, further
Preferably 0.5-5:1:0.01-0.5, preferably 0.5-2:1:0.01-0.1.
According to the present invention, the radical initiator can have multiple choices, it is preferable that the radical initiator is
Di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide, dibenzoyl peroxide, mistake
Methyl Ethyl Ketone Oxidation, cyclohexanone peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, dicetyl peroxydicarbonate
One of dicyclohexyl maleate, azodiisobutyronitrile, azobisisoheptonitrile, potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate are a variety of.
Wherein, the dosage of the radical initiator can carry out suitably according to required vinylidene fluoride analog copolymer
Selection, for example, in order to obtain weight average molecular weight be 50,000-2,000,000g/mol, preferably 100,000-1,000,000g/
Mol, more preferably 200,000-800,000g/mol are still more preferably the inclined difluoro second of 250,000-500,000g/mol
Vinyl copolymer, it is preferable that relative to single shown in monomer shown in monomer shown in formula (1-a), formula (2-a) and formula (3-a)
The total moles dosage of body, the dosage of the radical initiator are 0.001-5mol%, preferably 0.1-5mol%, more preferably
0.2-2mol%.
According to the present invention, the organic solvent can have multiple choices, it is preferable that the organic solvent is N- methyl pyrrole
Pyrrolidone, ethyl alcohol, methanol, acetonitrile, nitromethane, dimethyl sulfoxide, N,N-dimethylformamide, acetone, chloroform, methylene chloride,
One of ethyl acetate and tetrahydrofuran are a variety of, preferably N-Methyl pyrrolidone, dimethyl sulfoxide, ethyl alcohol, methanol, N, N-
One of dimethylformamide, acetone, chloroform and tetrahydrofuran are a variety of.
Wherein, the dosage of the organic solvent can change in a wider range, it is preferable that the formula relative to 100mmol
The total amount of monomer shown in (1-a), monomer shown in monomer and formula (3-a) shown in formula (2-a), the dosage of the organic solvent
For 10-1000mL, preferably 40-500mL.
In the case of, according to the invention it is preferred to, the condition of the copolyreaction includes: that temperature is 50-90 DEG C, time 5-
40h.Preferably, it is 60-85 DEG C that the condition of the copolyreaction, which includes: temperature, and the time is 10-30h (for example, 20-25h).
According to the present invention it is possible to first mix monomer, radical initiator and organic solvent shown in formula (1-a),
Temperature is then increased to the temperature of copolyreaction, is re-introduced into monomer shown in monomer shown in formula (2-a) and formula (3-a) to carry out
Copolyreaction.
According to the present invention, in order to be purified to vinylidene fluoride analog copolymer, method of the invention can also include: by
Product after the copolyreaction is separated by solid-liquid separation, and by gained solid-solution in ethyl alcohol, then uses Diethyl ether recrystallization, gained
Solid is vinylidene fluoride analog copolymer of the invention.
Third aspect present invention provides the vinylidene fluoride analog copolymer as made from the method for above-mentioned second aspect.
It should be understood that the vinylidene fluoride analog copolymer that this aspect of the invention provides is made by the above method,
Although will not do excessive description to the vinylidene fluoride analog copolymer herein, structure feature be can refer to above to inclined two
The description of vinyl fluoride analog copolymer.
Fourth aspect present invention provides above-mentioned vinylidene fluoride analog copolymer answering as binder in lithium ion battery
With.
The vinylidene fluoride analog copolymer that the present invention obtains can be molten well in huge polarity and nonpolar solvent
Solution；There is better tolerance to strong alkali environment simultaneously；In addition it can reduce influence of the binder for Ion transfer in pole piece；
It is therefore particularly suitable in lithium ion battery as binder.Such binder is generally used for preparation anode and cathode.
Fifth aspect present invention provides a kind of battery electrode, and the electrode includes: that electrode current collecting body and its surface are adhered to
Electrode material layer, the electrode material layer contain electrode active material and binder, and the binder contains above-mentioned inclined difluoro second
Vinyl copolymer.
According to the present invention, the content of the electrode active material and binder can change in a wider range, it is preferable that
Relative to the electrode active material of 100 parts by weight, the content of the binder is 1-20 parts by weight, preferably 2-15 parts by weight.
Conductive agent can also be contained in the electrode material layer, it is preferable that the electrode activity material relative to 100 parts by weight
Material, the content of the conductive agent are 1-20 parts by weight, preferably 5-15 parts by weight.
In accordance with the present invention it is preferred that the conductive agent is acetylene black, superconduction carbon, conductive carbon black, electrically conductive graphite, carbon nanometer
One of pipe and carbon nano-fiber are a variety of.
Wherein, the electrode can be anode, be also possible to cathode, when the electrode is anode, the electrode activity
Material is positive electrode active materials, and the electrode material layer of formation is positive electrode material layer；When the electrode is cathode, the electrode active
Property material be negative electrode active material, the electrode material layer of formation is negative electrode material layer, and the electrode active material is negative electrode material
Layer.
Wherein, the positive electrode active materials are preferably LiCoO2、LiNi0.5Mn1.5O4、LiNixCoyMnzO2(abbreviation NCM, often
That sees has NCM811, NCM622, NCM523 and NCM333), LiNixCoyAlzO2(abbreviation NCA, common are
LiNi0.8Co0.15Al0.05O2) and LiMPO4One of or it is a variety of, wherein 0 < x < 1,0 < y < 1,0 < z < 1, and x+y+z=1, M
For Fe, Co, Ni or Mn.
Wherein, the negative electrode active material is preferably one in graphite, active carbon, graphene, silicon and Si-C composite material
Kind is a variety of.
In accordance with the present invention it is preferred that the electrode material layer with a thickness of 10-200 μm (single side thickness).
According to the present invention, there is no any special restriction to the electrode current collecting body, the electricity of this field routine can be used
Pole collector, for example, copper foil, aluminium foil etc., thickness for example can be 1-100 μm.
Sixth aspect present invention provides the preparation method of battery electrode described in the 5th aspect, this method comprises:
(1) electrode slurry containing electrode active material, binder and optional conductive agent is provided；
(2) electrode slurry of step (1) is coated on electrode current collecting body, and dry, to be formed on electrode current collecting body
Electrode material layer.
According to the present invention, the electrode active material, the selection of optional conductive agent and binder and dosage are as above
Described, details are not described herein by the present invention.
According to the present invention, the solvent that the electrode slurry uses can have very wide selection, it is preferable that the electrode
Solvent used by slurry is N-Methyl pyrrolidone, ethyl alcohol, methanol, acetonitrile, nitromethane, dimethyl sulfoxide, N, N- dimethyl
One of formamide, acetone, chloroform, methylene chloride, ethyl acetate and tetrahydrofuran are a variety of, preferably N- crassitude
One of ketone, dimethyl sulfoxide, ethyl alcohol, methanol, N,N-dimethylformamide, acetone, chloroform and tetrahydrofuran are a variety of.
Wherein, for the dosage of the solvent, there is no particular limitation, such as the use of solvent used by the electrode slurry
Amount is so that the total concentration of electrode active material, optional conductive agent and binder is 20-80 weight %, preferably 30-60 weight
Measure %.
According to the present invention, in the preparation method of above-mentioned battery electrode, electrode slurry is coated on electrode current collecting body by step (2)
On, and drying can form electrode material layer on a current collector.Wherein, the electrode current collecting body is as described above, should
Dry temperature for example can be 50-70 DEG C, with drying.
Seventh aspect present invention provides a kind of lithium battery, which includes: anode, cathode, battery diaphragm and electrolyte,
In, the anode and/or cathode are above-mentioned battery electrode.
In accordance with the present invention it is preferred that the just extremely above-mentioned battery electrode is the situation of anode, the cathode is above-mentioned electricity
The case where pond electrode is cathode.
Wherein, the battery diaphragm and electrolyte all can be this field diaphragm and electrolyte that routinely use, the present invention
To this, there is no particular limitation.
For example, the battery diaphragm can be coated with PE the or PP diaphragm of PVDF-HFP for two sides, commercially available product can be.
For example, the electrolyte can be the organic solution of lithium salts, concentration for example can be 0.5-2mol/L, preferably
1-1.5mol/L.Wherein, lithium salts for example can be LiClO4(lithium perchlorate), LiPF6(lithium hexafluoro phosphate), LiBF4(tetrafluoro boron
Sour lithium), LiBOB (dioxalic acid lithium borate), LiN (SO2CF3)2(double trifluoro (methane sulfonic acid) imine lithiums), LiCF3SO3(fluoroform
Base Sulfonic Lithium) and LiN (SO2CF2CF3)2One of or it is a variety of.Used solvent for example can be vinylene carbonate
(VC), one of ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC)
Or it is a variety of, preferably EC:DMC:VC volume ratio be 1:0.5-2:0.01-0.05 mixed solvent.
The present invention will be described in detail by way of examples below.
Preparation example 1
Monomer is prepared according to upper reaction equation, specifically:
(1) p-chloro benzenesulfonamide and 2.3794g (20mmol) thionyl chloride, 1.3982g of 1.9164g (10mmol) are taken
(12mmol) chlorosulfonic acid reacts 12h at 100 DEG C, obtains compound 1a (2.6113g, yield 90%)；1H NMR (400MHz,
CDCl3, ppm), δ=7.87 (d, 2 × 1H), 7.55 (d, 2 × 1H), 2.0 (s, 1H).
(2) compound 1a and 2.1451g (12mmol) SbF of 2.9014g (10mmol) is taken312h is reacted at 60 DEG C, is obtained
To compound 1b (2.4632g, yield 90%)；1H NMR (400MHz, CDCl3, ppm), δ=7.87 (d, 2 × 1H), 7.55 (d,
2×1H)、2.0(s,1H)。
(3) compound 1b and 0.7389g (10mmol) Li of 2.7369g (10mmol) is taken2CO32h is reacted at 25 DEG C, is obtained
To compound 1c (2.7962g, yield 100%)；1H NMR (400MHz, CDCl3, ppm), δ=7.87 (d, 2 × 1H), 7.55
(d,2×1H)、2.0(s,1H)。
(4) it in the case where carrying out cooling with ice salt bath, takes the compound 1c of 2.7962g (10mmol) and is added
The tetrahydrofuran solution 10mL of 1.6015g (25mmol) n-BuLi.After the two is stirred 2h, it is slowly introducing thereto
The fluoro- 2- vinyl chloride gas of 1.4772g (15mmol) 1,1- bis- reacts 12h, obtains formula (1-a-1) compound represented
(2.7648g, yield 90%)；1H NMR (400MHz, CDCl3, ppm), δ=7.88 (d, 2 × 1H), 7.58 (d, 2 × 1H),
5.21(m,1H)。
(5) formula (1-a-1) compound represented and 1.6128g (11mmol) chlorination 1- second of 3.072g (10mmol) are taken
Base -3- methylimidazole reacts 12h at 25 DEG C, obtains formula (1-a-2) compound represented (3.7028g, yield 90%)；1H
NMR (400MHz, CDCl3, ppm), δ=8.94 (s, 1H), 7.88 (d, 2 × 1H), 7.74 (s, 1H), 7.67 (s, 1H), 7.58
(d,2×1H)、5.21(m,1H)、4.38(q,2H)、4.03(s,3H)、1.56(t,3H)。
Embodiment 1
The present embodiment is for illustrating vinylidene fluoride analog copolymer and preparation method thereof of the invention.
Take formula (1-a-1) compound represented of 6.144g (20mmol), the di-tert-butyl peroxide of 0.1mmol and
20mL acetonitrile carries out uniformly mixed.And vinylidene fluoride and hexafluoro third that molar ratio is 99:1 are passed through under heating stirring at 70 DEG C
The mixed gas (about 20mmol) of alkene.After gas is passed through process, it is further continued for reaction for 24 hours；Products therefrom is filtered, and by solid
It is dissolved with 10mL ethyl alcohol, 50mL ether is then added and is recrystallized, recrystallizes repeatedly three times, then obtained solid is carried out
Vacuum drying, obtains the vinylidene fluoride analog copolymer P1 of white powder；
Wherein, the weight average molecular weight of the vinylidene fluoride analog copolymer is 300,000g/mol, and molecular weight distributing index is
1.3, the molar ratio of structural unit shown in structural unit and formula (3) shown in structural unit, formula (2) shown in formula (1-1) is
1.01:1:0.01.
Embodiment 2
The present embodiment is for illustrating vinylidene fluoride analog copolymer and preparation method thereof of the invention.
Take formula (1-a-2) compound represented of 8.228g (20mmol), the benzoyl peroxide and 50mL second of 0.2mmol
Nitrile carries out uniformly mixed.And molar ratio is passed through under heating stirring at 80 DEG C as the vinylidene fluoride of 95:5 and mixing for hexafluoropropene
It closes gas (about 30mmol).After gas is passed through process, it is further continued for reaction 20h；Products therefrom is filtered, and by solid 10mL
Then ethyl alcohol dissolution is added 50mL ether and is recrystallized, recrystallized repeatedly three times, obtained solid is then carried out vacuum and is done
It is dry, obtain the vinylidene fluoride analog copolymer P2 of white powder；
Wherein, the weight average molecular weight of the vinylidene fluoride analog copolymer is 200,000g/mol, and molecular weight distributing index is
1.2, the molar ratio of structural unit shown in structural unit and formula (3) shown in structural unit, formula (2) shown in formula (1-2) is
0.7:1:0.05.
Embodiment 3
The present embodiment is for illustrating vinylidene fluoride analog copolymer and preparation method thereof of the invention.
According to method described in embodiment 1, unlike, the dosage of di-tert-butyl peroxide is 0.05mmol, inclined two
The time that the reaction was continued after vinyl fluoride and the mixed gas of hexafluoropropene are passed through is 15h；To obtain vinylidene fluoride class
Copolymer p 3；
Wherein, the weight average molecular weight of the vinylidene fluoride analog copolymer is 100,000g/mol, and molecular weight distributing index is
1.4。
Embodiment 4
The present embodiment is for illustrating vinylidene fluoride analog copolymer and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, the dosage of di-tert-butyl peroxide is 2mmol, inclined difluoro second
The time that the reaction was continued after the mixed gas of alkene and hexafluoropropene is passed through is 35h；To obtain the copolymerization of vinylidene fluoride class
Object P4；
Wherein, the weight average molecular weight of the vinylidene fluoride analog copolymer is 1,000,000g/mol, molecular weight distributing index
It is 1.5.
Comparative example 1
According to method described in embodiment 1, unlike, do not use formula (1-a-1) compound represented, but by inclined two
The mole dosage of vinyl fluoride and the mixed gas of hexafluoropropene is adjusted to 40mmol, to obtain vinylidene fluoride-hexafluoropropene
Copolymer DP1.
Wherein, the weight average molecular weight of DP1 is 300,000g/mol, molecular weight distributing index 1.32.
Test case 1
Dissolubility is tested, respectively vinylidene fluoride analog copolymer P1-P4 and DP1 and A Ke resulting to above-described embodiment
The dissolubility of the LBG type PVDF-HFP of Ma company in a solvent is tested, and the polymer of 0.5g is specifically dissolved in the phase of 10g
It answers in solvent, observation dissolution situation, the results are shown in Table 1.
Table 1
| Solvent | P1 | P2 | P3 | P4 | DP1 | LBG |
| N-Methyl pyrrolidone | It can be molten | It can be molten | It can be molten | It can be molten | It can be molten | It can be molten |
| Dimethyl sulfoxide | It can be molten | It can be molten | It can be molten | It can be molten | It can be molten | It can be molten |
| Methanol | It can be molten | It can be molten | It can be molten | It can be molten | It cannot be molten | It cannot be molten |
| Ethyl alcohol | It can be molten | It can be molten | It can be molten | It can be molten | It cannot be molten | It cannot be molten |
| N,N-dimethylformamide | It can be molten | It can be molten | It can be molten | It can be molten | It can be molten | It can be molten |
| Acetone | It can be molten | It can be molten | It can be molten | It can be molten | It cannot be molten | It cannot be molten |
| Chloroform | It can be molten | It can be molten | It can be molten | It can be molten | It cannot be molten | It cannot be molten |
| Tetrahydrofuran | It can be molten | It can be molten | It can be molten | It can be molten | It cannot be molten | It cannot be molten |
Can be seen that the resulting vinylidene fluoride analog copolymer of the present invention by the data of table 1 can be compared with multiple types
There is excellent dissolubility in solvent.
Test case 2
Alkali resistance test: the resulting vinylidene fluoride analog copolymer P1-P4 and DP1 and A Ke of above-described embodiment is taken respectively
LBG type each 0.5g of PVDF-HFP of Ma company, is then dissolved in the DMF solution containing 0.5g LiOH, and observing solution later is
No discoloration；It the results are shown in Table shown in 2.
Table 2
| Sample solution | P1 | P2 | P3 | P4 | DP1 | LBG |
| Whether solution changes color | It is no | It is no | It is no | It is no | It is | It is |
Can be seen that the resulting vinylidene fluoride analog copolymer of the present invention by the data of table 2 has excellent alkali resistance
Energy.
Positive plate preparation example 1-4
This preparation example is for illustrating battery electrode and preparation method thereof of the invention.
(1) respectively by the LiCoO of the above-mentioned vinylidene fluoride analog copolymer P1-P4 and 9g of 0.5g2, 0.5g acetylene black and 10g
Ethyl alcohol is uniformly dispersed with dispersion machine, obtains anode sizing agent；
(2) anode sizing agent is equably coated on aluminium foil (with a thickness of 18 μm) with coating machine, is then dried at 60 DEG C,
To obtain positive plate A1-A4, wherein the single side thickness of positive electrode material layer is about 200 μm.
Positive plate comparative example 1
According to method described in positive plate preparation example 1, unlike, using etc. weight comparative example 1 made from inclined difluoro
Ethylene-hexafluoropropylene copolymer DP1 replaces vinylidene fluoride analog copolymer P1, also, the N- crassitude of the weight such as use
Ketone replaces ethyl alcohol, to obtain positive plate DA1.
Positive plate comparative example 2
According to method described in positive plate preparation example 1, unlike, using etc. weight the LBG purchased from Arkema
Type PVDF-HFP replaces vinylidene fluoride analog copolymer P1, also, the N-Methyl pyrrolidone of the weight such as use replaces ethyl alcohol, from
And obtain positive plate DA2.
Negative electrode tab preparation example 1-4
This preparation example is for illustrating battery electrode and preparation method thereof of the invention.
(1) graphite of the above-mentioned vinylidene fluoride analog copolymer P1-P4 and 9g of 0.5g, 0.5g carbon nanotube (are purchased from respectively
Qingdao Hao Xin New Energy Technology Co., Ltd.) and 10g ethyl alcohol be uniformly dispersed with dispersion machine, obtain negative electrode slurry；
(2) negative electrode slurry is equably coated on aluminium foil (with a thickness of 18 μm) with coating machine, is then dried at 60 DEG C,
To obtain negative electrode tab B1-B4, wherein the thickness of negative electrode material layer is about 200 μm.
Negative electrode tab comparative example 1
According to method described in negative electrode tab preparation example 1, unlike, using etc. weight comparative example 1 made from inclined difluoro
Ethylene-hexafluoropropylene copolymer DP1 replaces vinylidene fluoride analog copolymer P1, also, the N- crassitude of the weight such as use
Ketone replaces ethyl alcohol, to obtain negative electrode tab DB1.
Negative electrode tab comparative example 2
According to method described in negative electrode tab preparation example 1, unlike, using etc. weight purchased from BASF AG
The water system butadiene-styrene rubber of the SD332 trade mark replaces vinylidene fluoride analog copolymer P1, also, the water of the weight such as use replaces ethyl alcohol,
To obtain negative electrode tab DB2.
Battery preparation example 1
This preparation example is for illustrating lithium battery of the invention.
By positive plate A1, negative electrode tab B1, PVDF-HFP two sides coat PP diaphragm (be purchased from Celgard company, PP basement membrane
With a thickness of 12 μm, for the single side of PVDF-HFP coating with a thickness of 2 μm, overall thickness is 16 μm) and LiPF6Concentration is the liquid of 1mol/L
State electrolyte (LiPF6/ EC-DMC-VC (volume ratio 1:1:0.02)) it is prepared into soft-package battery C1.
Battery preparation example 2
This preparation example is for illustrating lithium battery of the invention.
According to method described in battery preparation example 1, the difference is that, positive plate A1, negative electrode tab B2 are replaced using positive plate A2
Instead of negative electrode tab B1, soft-package battery C2 is made.
Battery preparation example 3
This preparation example is for illustrating lithium battery of the invention.
According to method described in battery preparation example 1, the difference is that, positive plate A1, negative electrode tab B3 are replaced using positive plate A3
Instead of negative electrode tab B1, soft-package battery C3 is made.
Battery preparation example 4
This preparation example is for illustrating lithium battery of the invention.
According to method described in battery preparation example 1, the difference is that, positive plate A1, negative electrode tab B4 are replaced using positive plate A4
Instead of negative electrode tab B1, soft-package battery C4 is made.
Battery comparative example 1
According to method described in battery preparation example 1, the difference is that, positive plate A1, negative electrode tab are replaced using positive plate DA1
DB1 replaces negative electrode tab B1, and soft-package battery DC1 is made.
Battery comparative example 2
According to method described in battery preparation example 1, the difference is that, positive plate A1, negative electrode tab are replaced using positive plate DA2
DB2 replaces negative electrode tab B1, and soft-package battery DC2 is made.
Test case 3
The high rate performance and cycle performance of upper battery are tested respectively, the results are shown in Table 3.
Wherein, high rate performance test process: by battery first with the multiplying power of 0.1C from 3.0V constant-current charge to 4.2V, then in
4.2V constant-voltage charge to 0.01C end, later stand 5 minutes, finally respectively with the multiplying power of 0.5C, 1C, 2C, 5C, 8C, 10C into
Row discharges into 3.0V.
Cycle performance test process: by battery first with the multiplying power of 2C from 3.0V constant-current charge to 4.2V, 5 points are stood later
Then clock is ended in 4.2V constant-voltage charge to 0.02C, is finally carried out discharging into 3.0V with the multiplying power of 2C, finally stand 5 minutes.
So circulation 500 times.
Table 3
It can be seen that using vinylidene fluoride analog copolymer of the invention by the data of table 3 as under binder, it can
Obtain the lithium battery of higher specific capacity and cycle performance.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (17)
1. a kind of vinylidene fluoride analog copolymer suitable for binder, which is characterized in that the copolymer contains shown in following formula (1)
Structural unit, structural unit shown in structural unit and formula (3) shown in formula (2)；
Wherein, Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-(CH2CH2O)m-、-(OCH2CH2)m-、-(CO)-
O- or-O- (CO)-, k are each independently the integer of 1-5, and m is each independently the integer of 1-20；
RfFor-ChF2h+1, h is the integer of 0-10；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i is the whole of 0-10
Number；
Cationic Y+For H+、Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Al3+, cation, formula shown in formula (4)
(5) cation shown in cation, formula shown in (6), cation, formula (9) institute shown in cation, formula (8) shown in formula (7)
The cation shown and any one in cation shown in formula (10):
Wherein, R1、R2、R3And R4It is each independently selected from the alkyl or-(CH of C1-C102CH2O)j-CH3, j is each independently 1-
10 integer.
2. copolymer according to claim 1, wherein Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-
(CH2CH2O)m-、-(OCH2CH2)m,-(CO)-O- or-O- (CO)-, k is each independently 1,2 or 3, and m is each independently 1-
10 integer；RfFor-ChF2h+1, h is the integer of 0-5；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i 0-5
Integer；R1、R2、R3And R4It is each independently selected from the alkyl or-(CH of C1-C52CH2O)j-CH3, j is each independently 1-5's
Integer；
Preferably, Z is each independently selected from singly-bound ,-CH2-、-CH2-CH2-、-CF2-、-CF2-CF2-、-CH2CH2O-、-
OCH2CH2,-(CO)-O- or-O- (CO)-；RfFor-F ,-CF3Or-CF2CF3, Rf1、Rf2And Rf3Be each independently-H ,-
CH3、-CH2CH3、-F、-CF3Or-CF2CF3；R1、R2、R3And R4Be each independently selected from methyl, ethyl, n-propyl, isopropyl,
Normal-butyl ,-CH2CH2O-CH3Or-(CH2CH2O)2-CH3。
3. copolymer according to claim 1 or 2, wherein structural unit shown in the formula (1) is tied shown in formula (2)
The molar ratio of structural unit shown in structure unit and formula (3) is 0.001-999:1:0.001-9, preferably 0.01-100:1:
0.005-5, more preferably 0.1-9:1:0.01-1 are still more preferably 0.5-5:1:0.01-0.5；
Preferably, the weight average molecular weight of the copolymer is 50,000-2,000,000g/mol, preferably 100,000-1,000,
000g/mol, more preferably 200,000-800,000g/mol.
4. a kind of preparation method of vinylidene fluoride analog copolymer, which is characterized in that this method comprises: being deposited in radical initiator
Under, in organic solvent, by monomer shown in monomer shown in monomer shown in formula (1-a), formula (2-a) and formula (3-a) into
Row copolyreaction, wherein
Formula (1-a)Formula (2-a) CF2=CH2, formula (3-a)
Wherein, Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-(CH2CH2O)m-、-(OCH2CH2)m-、-(CO)-
O- or-O- (CO)-, k are each independently the integer of 1-5, and m is each independently the integer of 1-20；
RfFor-ChF2h+1, h is the integer of 0-10；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i is the whole of 0-10
Number；
Cationic Y+For H+、Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、Al3+, cation, formula shown in formula (4)
(5) cation shown in cation, formula shown in (6), cation, formula (9) institute shown in cation, formula (8) shown in formula (7)
The cation shown and any one in cation shown in formula (10):
Wherein, R1、R2、R3And R4It is each independently selected from the alkyl or-(CH of C1-C102CH2O)j-CH3, j is each independently 1-
10 integer.
5. according to the method described in claim 4, wherein, Z is each independently selected from singly-bound ,-(CmH2m)-、-(CmF2m)-、-
(CH2CH2O)m-、-(OCH2CH2)m,-(CO)-O- or-O- (CO)-, k is each independently 1,2 or 3, and m is each independently 1-
10 integer；RfFor-ChF2h+1, h is the integer of 0-5；Rf1、Rf2And Rf3It is each independently-CiH2i+1Or-CiF2i+1, i 0-5
Integer；R1、R2、R3And R4It is each independently selected from the alkyl or-(CH of C1-C52CH2O)j-CH3, j is each independently 1-5's
Integer；
Preferably, Z is each independently selected from singly-bound ,-CH2-、-CH2-CH2-、-CF2-、-CF2-CF2-、-CH2CH2O-、-
OCH2CH2,-(CO)-O- or-O- (CO)-；RfFor-F ,-CF3Or-CF2CF3, Rf1、Rf2And Rf3Be each independently-H ,-
CH3、-CH2CH3、-F、-CF3Or-CF2CF3；R1、R2、R3And R4Be each independently selected from methyl, ethyl, n-propyl, isopropyl,
Normal-butyl ,-CH2CH2O-CH3Or-(CH2CH2O)2-CH3。
6. method according to claim 4 or 5, wherein monomer shown in formula (1-a), monomer and formula shown in formula (2-a)
The molar ratio of the dosage of monomer shown in (3-a) be 0.001-999:1:0.001-9, preferably 0.01-100:1:0.005-5,
More preferably 0.1-9:1:0.01-1 is still more preferably 0.5-5:1:0.01-0.5.
7. method according to any one of claims 4 to 6, wherein the radical initiator is di-t-butyl peroxide
Compound, dicumyl peroxide, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide, dibenzoyl peroxide, methyl ethyl ketone peroxide,
Cyclohexanone peroxide, peroxidized t-butyl perbenzoate, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, idol
One of nitrogen bis-isobutyronitrile, azobisisoheptonitrile, potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate are a variety of；
Preferably, always rubbing relative to monomer shown in monomer shown in monomer shown in formula (1-a), formula (2-a) and formula (3-a)
That dosage, the dosage of the radical initiator are 0.001-5mol%, preferably 0.1-5mol%, more preferably 0.2-
2mol%.
8. the method according to any one of claim 4-7, wherein the organic solvent be N-Methyl pyrrolidone,
Ethyl alcohol, methanol, acetonitrile, nitromethane, dimethyl sulfoxide, N,N-dimethylformamide, acetone, chloroform, methylene chloride, ethyl acetate
With one of tetrahydrofuran or a variety of, preferably N-Methyl pyrrolidone, dimethyl sulfoxide, ethyl alcohol, methanol, N, N- dimethyl methyl
One of amide, acetone, chloroform and tetrahydrofuran are a variety of；
Preferably, relative to shown in monomer shown in monomer shown in the formula of 100mmol (1-a), formula (2-a) and formula (3-a)
The total amount of monomer, the dosage of the organic solvent are 10-1000mL.
9. the method according to any one of claim 4-8, wherein the condition of the copolyreaction includes: that temperature is
50-90 DEG C, time 5-40h.
10. vinylidene fluoride analog copolymer made from the method as described in any one of claim 4-9.
11. vinylidene fluoride analog copolymer described in any one of claim 1-3 and 10 is in lithium ion battery as viscous
Tie the application of agent.
12. a kind of battery electrode, the electrode includes: the electrode material layer of electrode current collecting body and the attachment of its surface, the electrode
Material layer contains electrode active material and binder, and the binder contains described in any one of claim 1-3 and 10
Vinylidene fluoride analog copolymer.
13. battery electrode according to claim 12, wherein described viscous relative to the electrode active material of 100 parts by weight
The content for tying agent is 1-20 parts by weight, preferably 2-15 parts by weight.
14. battery electrode according to claim 12 or 13, wherein also contain conductive agent, phase in the electrode material layer
For the electrode active material of 100 parts by weight, the content of the conductive agent is 1-20 parts by weight, preferably 5-15 parts by weight；
Preferably, the conductive agent is in acetylene black, superconduction carbon, conductive carbon black, electrically conductive graphite, carbon nanotube and carbon nano-fiber
It is one or more；
Preferably, when the electrode is anode, the electrode active material is positive electrode active materials, the positive electrode active materials
For LiCoO2、LiNi0.5Mn1.5O4、LiNixCoyMnzO2、LiNixCoyAlzO2And LiMPO4One of or it is a variety of, wherein 0 < x <
1,0 < y < 1,0 < z < 1, and x+y+z=1, M Fe, Co, Ni or Mn；When the electrode is cathode, the electrode active material
For negative electrode active material, the negative electrode active material is one of graphite, active carbon, graphene, silicon and Si-C composite material
Or it is a variety of；
Preferably, the electrode material layer with a thickness of 10-200 μm.
15. the preparation method of battery electrode described in any one of claim 12-14, this method comprises:
(1) electrode slurry containing electrode active material, binder and optional conductive agent is provided；
(2) electrode slurry of step (1) is coated on electrode current collecting body, and dry, to form electrode on electrode current collecting body
Material layer.
16. preparation method according to claim 15, wherein solvent used by the electrode slurry is N- methylpyrrole
One of alkanone, dimethyl sulfoxide, ethyl alcohol, methanol, N,N-dimethylformamide, acetone, chloroform and tetrahydrofuran are a variety of；
Preferably, the dosage of solvent used by the electrode slurry makes electrode active material, optional conductive agent and bonding
The total concentration of agent is 20-80 weight %, preferably 30-60 weight %.
17. a kind of lithium battery, which includes: anode, cathode and electrolyte, wherein the anode and/or cathode are wanted for right
Seek battery electrode described in any one of 12-14.
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