CN110323444A - The lithium ion anode water-based binder of one kind containing pyridine groups and preparation method thereof, lithium ion secondary battery - Google Patents
The lithium ion anode water-based binder of one kind containing pyridine groups and preparation method thereof, lithium ion secondary battery Download PDFInfo
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- CN110323444A CN110323444A CN201910469552.XA CN201910469552A CN110323444A CN 110323444 A CN110323444 A CN 110323444A CN 201910469552 A CN201910469552 A CN 201910469552A CN 110323444 A CN110323444 A CN 110323444A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Lithium ion anode water-based binder the present invention provides one kind containing pyridine groups is the alcoholysis product of polyethylene maleic anhydride and pyridinemethanol.The present invention also provides the preparation methods of the binder: being added pyridinemethanol into polyethylene maleic anhydride solution, after heating reaction, using lithium hydroxide solution lithiumation and removes solvent and obtain.The present invention also provides the lithium ion secondary batteries for using the binder.It include ester group, carboxylic acid, carboxylic acid lithium and pyridine groups in water-based binder structure of the invention, excellent caking property can be provided, the presence of molecule interchain hydrogen bond action can preferably maintain the stability of electrode, while the introducing of carboxylic acid lithium and pyridine groups can promote ion mobility.The LiFePO 4 button cell battery impedance assembled using such binder is smaller, specific discharge capacity is higher, comprehensive performance has surmounted battery made by marketed adhesives currently on the market, especially in terms of fast charge, 3000 times can be carried out under the multiplying power of 20C and stablizes circulation.
Description
Technical field
The invention belongs to electrochemical technology fields, more particularly to a kind of lithium ion anode water-based binder containing pyridine groups
And preparation method thereof and using the binder lithium ion secondary battery.
Background technique
Lithium ion battery (LIB) is not only widely used in portable electronic device as one of most important energy storage device
It is nowadays also preferred as the power device of electric car with small intelligent equipment.In lithium ion battery composition, binders for electrodes
It is that electrode active material, conductive agent are securely bonded together and are adhered to the high molecular material on collector by one kind, contains
Less (1%~10%) is measured, but plays highly important effect.Presently, most popular polymeric binder
It is PVDF (polyvinylidene fluoride), which needs to be dissolved in toxic solvent NMP (N-Methyl pyrrolidone, 202 DEG C of boiling point)
In.Following problem can be brought when using oiliness binder PVDF system: firstly, can generate when producing PVDF a large amount of
By-product HF, leads to environmental pollution；Secondly, the dissolution of PVDF need to carry out under heating, very slowly when making solvent with NMP
And energy is expended, furthermore NMP is expensive, and recycling is difficult, spends human and material resources；Finally, in battery charge and discharge process, PVDF
The formation of LiF and HF can be induced when contacting with electrolyte, this can accelerate the decomposition of binder so as to cause the quick of battery performance
Decline.With the fast development of artificial intelligence and microelectronic product, fast charge and the two features of long circulating are by as battery industry
Important referential data, and PVDF is unable to satisfy emerging product as the theme that business bonding agent had both been unfavorable for green energy resource
It is required that.Water-based binder accounts for 30% or so of entire lithium electricity binder consumption at present, is predicted according to associated mechanisms, the five-year year
Compound speedup will be more than 30%.Therefore, develop water-soluble binder of new generation and have become the hot spot of industry and the call in epoch.
Summary of the invention
In view of this, the present invention provides a kind of novel lithium ion anode water-based binder containing pyridine groups,
Using the polymer containing acid anhydrides as main chain in structure, ester group is formed after reacting with pyridinemethanol, pyridine groups can be such that structure has more
Good mechanical property, moreover it is possible to promote the evenly dispersed of conductive agent carbon and make to constitute more stable conductive mesh between electrode activity particle
Network, in addition, unreacted carboxyl structure included in binder can also provide hydrogen bond and lithium ion conduction site to increase pole
The stability of chip architecture and the migration for promoting ion, are conducive to the promotion of circulation and high rate performance.
When using the water soluble adhesive, a small amount of deionized water only need to be added, stirring several minutes under room temperature can be complete
Dissolution, it is convenient, efficient, at low cost, pollution-free.In terms of caking property intensity, in the case where same amount, bonding of the invention
Agent caking property is all larger than marketed adhesives, establishes its bonding advantage.In terms of dosage, it is only necessary to which 3% binder can be kept
The integrality of battery and the stability of performance, and this is only miniature in the laboratory that environment and technology are subject to certain restrictions
The level reached in the case of production, if placing it in commercialization flow line production, dosage estimation can be reduced to 1% or so,
Its cost can drop to the 50% or less of PVDF simultaneously.In terms of the carrying capacity of face, button cell can be in 2mgcm-2High carrying capacity
In the case of still keep excellent high rate performance, embody its preferable commercial value.
The first aspect of the invention provides a kind of novel lithium ion anode water-based binder containing pyridine groups,
The binder is the alcoholysis esterification products PMY of polymer and pyridinemethanol containing acid anhydrides, and the polymer containing acid anhydrides is poly-
Ethylene maleic acid acid anhydride, the pyridinemethanol are 2- pyridinemethanol or 3- pyridinemethanol；Wherein, the structural formula of binder PMY are as follows:
The structural formula of polyethylene maleic anhydride are as follows:
Wherein, Py is 2- pyridyl groupOr 3- pyridyl groupX >=1, y >=1, z >=1, k >=1, m
>=1, n >=1；For polyethylene maleic anhydride, as m ≠ n, which is blending type polyethylene maleic anhydride, i.e. polyethylene-
Co- maleic anhydride；As m=n=1, which is alternate type polyethylene maleic anhydride, i.e. polyethylene-Alt- maleic anhydride
Further, the molar content of pyridine groups is 10%~50% in the binder PMY side chain, the binder
Carboxylic acid is partial lithiation in PMY side chain, that is, exists simultaneously carboxylic acid and carboxylic acid lithium, and carboxyl (includes carboxylic acid lithium and carboxylic in side chain
Acid) molar content be 50%~90%.
Another aspect of the present invention provides a kind of above-mentioned lithium ion anode water-based binder PMY containing pyridine groups
Preparation method, step are as follows:
The polyethylene maleic anhydride and pyridinemethanol of certain mol proportion example are weighed, organic solvent is added and catalyst is added
The obtained product of reaction is added to stirring and dissolving in a certain amount of LiOH aqueous solution and carries out lithiumation by thermal response, then go from
It dialyses in sub- water, can be obtained binder PMY after dry.For convenience of explanation, PMY series binder has following four classes: when making
When with 2- pyridinemethanol and polyethylene-Alt- maleic anhydride, gained binder is denoted as PMY2；When use 3- pyridinemethanol and poly- second
When alkene-Alt- maleic anhydride, gained binder is denoted as PMY3；When using 2- pyridinemethanol and polyethylene-Co- maleic anhydride,
Gained binder is denoted as PMY2 '；When using 3- pyridinemethanol and polyethylene-Co- maleic anhydride, gained binder is denoted as
PMY3’。
Further, the mole of the pyridinemethanol be 3 times of mole of acid anhydrides in polyethylene maleic anhydride or
More than, the organic solvent is n,N-Dimethylformamide (DMF), and the catalyst is p-methyl benzenesulfonic acid.
Further, the amount of the substance of used lithium hydroxide and binder prepare used poly- second during lithiumation
The content of acid anhydrides is equal in alkene maleic anhydride, and the carboxylic acid in guarantee system is in partial lithiation state, avoids binder because excessively
Lithiumation and become alkalinity.
In order to verify the generation of product, the present invention is using nuclear-magnetism and infrared is detected.In nucleus magnetic hydrogen spectrum, occur
Pyridine-CH in the absorption (7.8~8.4ppm) of low field and ester group2Characteristic absorption (~5.2ppm)；In infrared, acid anhydrides
Characteristic peak (1820cm-1) disappear, occur in slightly lower wavenumber region new carboxylic acid and carboxylate characteristic absorption (1745~
1630cm-1).Structural analysis shows to be esterified going on smoothly for alcoholysis.
The third aspect of the invention, provides lithium ion secondary cell, and the lithium ion secondary battery includes just
Pole material, negative electrode material, electrolyte, diaphragm and battery case, the positive electrode is by active material, conductive material and above-mentioned
The binder of preparation is constituted.The preparation method of positive electrode includes the following steps:
The binder PMY of a certain amount of above-mentioned preparation is weighed in 10ml beaker, appropriate amount of deionized water dissolution is added dropwise, then
Active material and conductive material is added into beaker, stirs 12h under room temperature, is prepared into anode sizing agent.Then in current collector aluminum foil
Upper coating anode sizing agent, and dried, it is sliced after the completion of dry and is assembled into button cell.
Further, active material described in above-mentioned technical proposal is LiFePO 4 (LFP), and conductive material is acetylene
It is black.
Further, the total mass fraction of bonding agent PMY is 3%~10% in above-mentioned technical proposal, the quality of acetylene black
Score is 10%~20%.
Compared with prior art, the invention has the following beneficial effects:
(1) preparation method of binder provided by the invention is simple, at low cost, and non-toxic by-products generate；
(2) solvent needed for binder provided by the invention is deionized water, cheap and environmentally protective；
(3) nmp solvent that marketed adhesives use, solution rate is slow and needs to heat, and binder provided by the invention
Without heating and solution rate it is fast, time and resource can be saved；
(4) contain ester group, carboxyl isopolarity group in binder provided by the invention, can also form hydrogen between strand
Key, the presence of hydrogen bond action can preferably maintain the stability of electrode, therefore caking property is good, very low (about 3%) in content
In the case where be also able to maintain the integrality of electrode structure；
(5) presence of carboxylic acid group does not have an impact the thermal stability of the binder in binder provided by the invention, should
Class binder good thermal stability, thermal decomposition temperature meet the requirement of electrode preparation and battery applications at 200 DEG C or more；
(6) pyridine groups in adhesive structure of the invention can be carried out preferably with carbon dust-active material composite particles
Effect, advantageously reduces the reuniting effect of active material particle during long circulating；
(7) lithium ion battery of binder assembling through the invention has on high rate performance compared with marketed adhesives PVDF
Very big breakthrough still can reach 60% (100mAhg of its theoretical capacity under 20C high current density-1)；
(8) through the invention binder assembling lithium ion battery coulombic efficiency it is very high (intimate 100%),
Under 20C high current density after 3000 circle of circulation, 99% or more specific discharge capacity is still kept, current commercial level has been surmounted,
Realize the leap of performance；
(9) lithium ion battery of binder assembling through the invention is in high face carrying capacity (about 2mgcm-2) the case where
Under, it is still able to maintain preferable high rate performance, this property implies that it has great application prospect；
(10) lithium ion battery of binder assembling through the invention is compared to using marketed adhesives PVDF to make
Lithium ion battery impedance is smaller, and specific discharge capacity is higher, and more preferably, comprehensive performance performance is superior for high rate performance and cyclical stability.
To sum up, the lithium ion battery excellent combination property of binder provided by the invention assembling, cost of manufacture are cheap, use
High-efficiency environment friendly, safety non-pollution, especially its fast charging and discharging characteristic, have a good application prospect.
Detailed description of the invention
Fig. 1 is the reaction equation of 1 binder PMY2 synthesis step of the embodiment of the present invention.
Fig. 2 is impedance contrast figure of the lithium ion battery of the production of embodiment 1 before and after the circle of circulation 3000.
Fig. 3 is cycle performance of battery figure of the lithium ion battery of the production of embodiment 1 under 20C high current density.
Fig. 4 is cycle performance of battery figure of the lithium ion battery of the production of embodiment 2 under 20C high current density.
Fig. 5 is the reaction equation of 4 binder PMY3 synthesis step of the embodiment of the present invention.
Fig. 6 is impedance contrast figure of the lithium ion battery of the production of embodiment 4 before and after the circle of circulation 3000.
Fig. 7 is cycle performance of battery figure of the lithium ion battery of the production of embodiment 4 under 20C high current density.
Fig. 8 is binder PMY2 obtained in embodiment 1, binder PMY3 obtained and reference examples 1 use in embodiment 4
Marketed adhesives PVDF peel strength figure.
Fig. 9 is the lithium ion battery multiplying power of the lithium ion battery that embodiment 1 makes and the lithium ion battery that reference examples 1 make
Performance map.
Figure 10 is the lithium ion battery times of the lithium ion battery that embodiment 4 makes and the lithium ion battery that reference examples 1 make
The performance map of rate.
Specific embodiment
Below by by specific embodiment, reference examples and its list in the present invention program preparation method, prepared
The content of journey and wherein material makees more deep elaboration.Following example is preferred embodiment in the present invention, unlimited
The range of system in the present invention, those skilled in the art can be used technology disclosed above and be adjusted and do accordingly
Change but is all under the jurisdiction of the content in the present invention.In the case where not departing from the method for the present invention and technology, side according to the present invention
Method does any simple transformation with technology or equivalence changes are within the scope of the invention.
Embodiment 1:
The present embodiment is a kind of lithium ion anode water-based binder containing pyridine groups and preparation method thereof and comprising it
Lithium ion secondary battery.
The preparation process of above-mentioned lithium ion anode water-based binder is specific as follows:
0.6303g polyethylene-Alt- maleic anhydride and 0.1672g p-methyl benzenesulfonic acid are weighed in flask, 30ml is added
Solvent n,N-Dimethylformamide (DMF) and 1.92ml 2- pyridinemethanol (anhydride unit and 2- pyridine in polyethylene maleic anhydride
The molar ratio of methanol be 1:4), be warming up to after stirring and dissolving at room temperature 100 DEG C carry out reaction 12h after, in acetone sedimentation obtain
Solid；It weighs 0.1g anhydrous lithium hydroxide and prepares lithium hydroxide solution in 50ml deionized water, consolidate what above-mentioned sedimentation obtained
Body is added thereto, and stirring 3h makes its abundant lithiumation, and then solution is transferred in bag filter with deionized water dialysis 48h；It will dialysis
Up to binder PMY2 after product afterwards is dry, yield 82%, pyridine grafting rate is 17%；The reaction mechanism mechanism of reaction is as shown in Figure 1.
Polyethylene maleic anhydride used in the present embodiment 1 is alternate type polyethylene maleic anhydride, molecular weight MnIt is 100,
000~500,000D.
The anode material for lithium-ion batteries preparation step of the present embodiment 1 is as follows:
By 0.2102g LiFePO 4 (LiFePO4), 0.0601g acetylene black, above-mentioned synthesis 0.0302g binder
PMY2 is made anode sizing agent, is coated according to 70wt%, the ratio of 20wt%, 10wt%, and collector is aluminium foil, and coating is completed
After be firstly placed on a conventional oven in 60 DEG C of dry 6h, with vacuum drying oven, dry to be cut into 15mm for 24 hours, after the completion of dry straight in 80 DEG C later
The circular electric pole piece of diameter.
Circular electric pole piece made from embodiment 1 is assembled into CR2025 button cell, wherein used cathode is metal
Lithium piece, diaphragm are polypropylene screen (PP films), and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Fig. 2 is impedance contrast figure of the lithium ion battery of the production of embodiment 1 before and after the circle of circulation 3000, can be seen by Fig. 2
Out, it is 180 Ω by the Charge-transfer resistance of the binder PMY2 battery made before circulating battery, and is followed by 3000 circles
After ring, since binder PMY2 constructs preferable electrons/ions conduction pathway in the battery, battery resistance is significantly reduced
Anti-, the battery high frequency region semicircle impedance of binder PMY2 production reduces most 6 Ω.
Fig. 3 is cycle performance of battery figure of the lithium ion battery of the production of embodiment 1 under 20C high current density, can by Fig. 3
96mAh g is up to the battery first discharge specific capacity for finding out that embodiment 1 makes-1, and the 600 circle specific discharge capacity before circulation
In the state of rising, the polarizing voltage of this and battery has close relationship；And coulombic efficiency is also very high by intimate 100%.
After the circle of circulating battery 3000, specific discharge capacity and initial discharge capacity maintain almost unchanged state, this very excellent
Cyclical stability further demonstrate binder PMY2 at higher current densities and can be improved de-/embedding lithium speed of electrode material
And the integrality of pole piece.
Embodiment 2:
By 0.2251g LiFePO 4 (LiFePO4), the 0.0151g that synthesizes of 0.0602g acetylene black, above-described embodiment 1 it is viscous
Agent PMY2 is tied according to 75wt%, the ratio of 20wt%, 5wt% are made anode sizing agent, are coated, and collector is aluminium foil, coating
It is firstly placed on a conventional oven after the completion in 60 DEG C of dry 6h, vacuum drying oven is used for 24 hours, to be cut into after the completion of dry in 80 DEG C of dryings later
The circular electric pole piece of 15mm diameter.
Circular electric pole piece made from embodiment 2 is assembled into CR2025 button cell, wherein used cathode is metal
Lithium piece, diaphragm are PP films, and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Fig. 4 is cycle performance of battery figure of the lithium ion battery of the production of embodiment 2 under 20C high current density.It can from Fig. 4
Although electrode uses 5% binder PMY2 in the battery to find out the production of embodiment 2, still achieve very excellent
As a result.
Embodiment 3:
By 0.2310g LiFePO 4 (LiFePO4), the 0.0092g that synthesizes of 0.0601g acetylene black, above-described embodiment 1 it is viscous
Agent PMY2 is tied according to 77wt%, the ratio of 20wt%, 3wt% are made anode sizing agent, are coated, and collector is aluminium foil, coating
It is firstly placed on a conventional oven after the completion in 60 DEG C of dry 6h, vacuum drying oven is used for 24 hours, to be cut into after the completion of dry in 80 DEG C of dryings later
The circular electric pole piece of 15mm diameter.
Circular electric pole piece made from embodiment 3 is assembled into CR2025 button cell, wherein used cathode is metal
Lithium piece, diaphragm are PP films, and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Embodiment 4:
The present embodiment is a kind of lithium ion anode water-based binder containing pyridine groups and preparation method thereof and comprising it
Lithium secondary battery.
The preparation process of above-mentioned lithium ion anode water-based binder is specific as follows:
0.6306g polyethylene-Alt- maleic anhydride and 0.1673g p-methyl benzenesulfonic acid are weighed in flask, 30ml is added
Solvent DMF and 1.92ml 3- pyridinemethanol (molar ratio of anhydride unit and 3- pyridinemethanol is 1 in polyethylene maleic anhydride:
4) 100 DEG C, are warming up to after stirring and dissolving at room temperature and carries out reaction 12h, product is evaporated removing on revolving instrument after the reaction was completed
Solvent；It weighs 0.1g anhydrous lithium hydroxide and prepares lithium hydroxide solution in 50ml deionized water, be added to product obtained above
In, stirring 3h makes its abundant lithiumation, and then solution is transferred in bag filter with deionized water dialysis 48h；By the product after dialysis
Up to binder PMY3 after drying, yield 77%, grafting rate 25%, the reaction mechanism mechanism of reaction is as shown in Figure 5.
Polyethylene maleic anhydride used in the present embodiment 4 is alternate type polyethylene maleic anhydride, molecular weight MnIt is 100,
000~500,000D.
The anode material for lithium-ion batteries preparation step of the present embodiment 4 is as follows:
By 0.2104g LiFePO 4 (LiFePO4), 0.0603g acetylene black, above-mentioned synthesis 0.0301g binder
PMY3 is made anode sizing agent, is coated according to 70wt%, the ratio of 20wt%, 10wt%, and collector is aluminium foil, and coating is completed
After be firstly placed on a conventional oven in 60 DEG C of dry 6h, with vacuum drying oven, dry to be cut into 15mm for 24 hours, after the completion of dry straight in 80 DEG C later
The circular electric pole piece of diameter.
Circular electric pole piece made from embodiment 4 is assembled into CR2025 button cell, wherein used cathode is metal
Lithium piece, diaphragm are PP films, and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Fig. 6 is impedance contrast figure of the lithium ion battery of the production of embodiment 4 before and after the circle of circulation 3000, can be seen by Fig. 6
Out, it is 190 Ω by the Charge-transfer resistance of the binder PMY3 battery made before circulating battery, and is followed by 3000 circles
After ring, since binder PMY3 constructs preferable electrons/ions conduction pathway in the battery, battery resistance is significantly reduced
Anti-, the battery high frequency region semicircle impedance of PMY3 production reduces most 15 Ω.
Fig. 7 is cycle performance of battery figure of the lithium ion battery of the production of embodiment 4 under 20C high current density.By in Fig. 7
It can be seen that the battery first discharge specific capacity that embodiment 4 makes is 76mAh g-1, with the increase of cycle-index, discharge specific volume
Amount has obvious rising without reducing instead, and 85mAh g has been up to when being recycled to 3000 circle-1, illustrate between electrode system each component
Interface impedance is optimized, and polarization reduces, while electrode system keeps good during long circulating.
Embodiment 5:
By 0.2252g LiFePO 4 (LiFePO4), the 0.0152g that synthesizes of 0.0601g acetylene black, above-described embodiment 4 it is viscous
Agent PMY3 is tied according to 75wt%, the ratio of 20wt%, 5wt% are made anode sizing agent, are coated, and collector is aluminium foil, coating
It is firstly placed on a conventional oven after the completion in 60 DEG C of dry 6h, vacuum drying oven is used for 24 hours, to be cut into after the completion of dry in 80 DEG C of dryings later
The circular electric pole piece of 15mm diameter.
Circular electric pole piece made from embodiment 5 is assembled into CR2025 button cell, wherein used cathode is metal
Lithium piece, diaphragm are PP films, and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Embodiment 6:
The present embodiment is a kind of lithium ion anode water-based binder containing pyridine groups and preparation method thereof and comprising it
Lithium secondary battery.
The preparation process of above-mentioned lithium ion anode water-based binder is specific as follows:
0.4514g polyethylene maleic anhydride and 0.1130g p-methyl benzenesulfonic acid are weighed in flask, 30ml solvent is added
DMF and 0.6540g 3- pyridinemethanol (molar ratio of anhydride unit and 3- pyridinemethanol is 1:3 in polyethylene maleic anhydride), room
100 DEG C are warming up to after the lower stirring and dissolving of temperature and carries out reaction 12h, and product is evaporated removing solvent on revolving instrument after the reaction was completed；
It weighs 0.0020mg anhydrous lithium hydroxide and prepares lithium hydroxide solution in 100ml deionized water, be added to product obtained above
In, stirring 3h makes its abundant lithiumation, and then solution is transferred in bag filter with deionized water dialysis 48h；By the product after dialysis
Up to binder PMY3 ' after drying.
Polyethylene maleic anhydride used in the present embodiment 6 is blending type polyethylene maleic anhydride, wherein mole of acid anhydrides
Content is 18%；Molecular weight MnFor 50,000~200,000D.
The anode material for lithium-ion batteries preparation step of the present embodiment 6 is as follows:
By 0.2100g LiFePO 4 (LiFePO4), 0.0601g acetylene black, above-mentioned synthesis 0.0301g binder
PMY3 ' is made anode sizing agent, is coated, collector is aluminium foil, has been coated with according to 70wt%, the ratio of 20wt%, 10wt%
It is firstly placed on a conventional oven after in 60 DEG C of dry 6h, vacuum drying oven is used for 24 hours, 15mm to be cut into after the completion of dry in 80 DEG C of dryings later
The circular electric pole piece of diameter.
Circular electric pole piece made from embodiment 6 is assembled into CR2025 button cell, wherein used cathode is metal
Lithium piece, diaphragm are PP films, and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Embodiment 7:
The present embodiment is a kind of lithium ion anode water-based binder containing pyridine groups and preparation method thereof and comprising it
Lithium secondary battery.
The preparation process of above-mentioned lithium ion anode water-based binder is specific as follows:
0.9035g polyethylene maleic anhydride and 0.2259g p-methyl benzenesulfonic acid are weighed in flask, 50ml solvent is added
DMF and 1.3080g 2- pyridinemethanol (molar ratio of anhydride unit and 2- pyridinemethanol is 1:3 in polyethylene maleic anhydride), room
100 DEG C are warming up to after the lower stirring and dissolving of temperature and carries out reaction 12h, and product is evaporated removing solvent on revolving instrument after the reaction was completed；
It weighs 0.0803g anhydrous lithium hydroxide and prepares lithium hydroxide solution in 100ml deionized water, be added to product obtained above
In, stirring 3h makes its abundant lithiumation, and then solution is transferred in bag filter with deionized water dialysis 48h；By the product after dialysis
Up to binder PMY2 ' after drying.
Polyethylene maleic anhydride used in the present embodiment 7 is blending type polyethylene maleic anhydride, wherein mole of acid anhydrides
Content is 18%；Molecular weight MnFor 50,000~200,000D.
The anode material for lithium-ion batteries preparation step of the present embodiment 7 is as follows:
By 0.2105g LiFePO 4 (LiFePO4), 0.0601g acetylene black, above-mentioned synthesis 0.0301g binder
PMY2 ' is made anode sizing agent, is coated, collector is aluminium foil, has been coated with according to 70wt%, the ratio of 20wt%, 10wt%
It is firstly placed on a conventional oven after in 60 DEG C of dry 6h, vacuum drying oven is used for 24 hours, 15mm to be cut into after the completion of dry in 80 DEG C of dryings later
The circular electric pole piece of diameter.
Circular electric pole piece made from embodiment 7 is assembled into CR2025 button cell, wherein used cathode is metal
Lithium piece, diaphragm are PP films, and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Reference examples 1:
The specific embodiment of this reference examples 1 is the bonding by the binder PMY2 of above-described embodiment 1-3 and embodiment 4-5
Agent PMY3 is changed to marketed adhesives PVDF production positive electrode and is assembled into button cell and probes into its electrochemical behavior.
The anode material for lithium-ion batteries preparation step of this reference examples 1 is as follows:
By 0.2103g LiFePO 4 (LiFePO4), 0.0604g acetylene black, 0.0302g PVDF according to 70wt%,
Anode sizing agent is made in the ratio of 20wt%, 10wt%, is coated, and collector is aluminium foil, and common baking is firstly placed on after the completion of coating
Case is placed in vacuum drying oven later in 80 DEG C of dryings for 24 hours in 60 DEG C of dry 6h, the circular electric of 15mm diameter is cut into after the completion of dry
Pole piece.
Circular electric pole piece obtained above is assembled into CR2025 button cell, wherein used cathode is lithium metal
Piece, diaphragm are polypropylene screen (PP films), and electrolyte solution is 1M LiPF6EC/DMC (1:1, vol%).
Binder PMY2 obtained in embodiment 1, the quotient that binder PMY3 obtained and reference examples 1 use in embodiment 4
The peel strength figure of industry binder PVDF is as shown in figure 8, binder PMY2, binder PMY3, binder as seen from Figure 8
The peel strength of PVDF is respectively 290N m-1、270N m-1、240N m-1, it can be seen that binder PMY2 that the present invention makes,
The viscosity of PMY3 will be apparently higher than marketed adhesives.
Fig. 9 is the lithium ion battery multiplying power of the lithium ion battery that embodiment 1 makes and the lithium ion battery that reference examples 1 make
Performance map, Figure 10 is the lithium ion battery times of the lithium ion battery that embodiment 4 makes and the lithium ion battery that reference examples 1 make
The performance map of rate, in Fig. 9 and Figure 10, when current density is 1C, 5C, 10C, 20C, by binder PMY2 and binder PMY3 system
The battery of work has on specific discharge capacity compared to marketed adhesives PVDF obviously to be promoted, and bonding has further been confirmed
Agent PMY2 and binder PMY3 is at higher current densities to the ability for keeping pole piece integrality, to entire electrification under high magnification
The ability for learning the electrons/ions conduction pathway reduction battery impedance of system construction makes battery show superior performance.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of lithium ion anode water-based binder containing pyridine groups, which is characterized in that the binder is polyethylene Malaysia
The alcoholysis esterification products of acid anhydrides and pyridinemethanol, the pyridinemethanol are 2- pyridinemethanol or 3- pyridinemethanol；Wherein, binder
Structural formula are as follows:
The structural formula of polyethylene maleic anhydride are as follows:
Wherein, Py is 2- pyridyl group or 3- pyridyl group；X >=1, y >=1, z >=1, k >=1, m >=1, n >=1；For polyethylene horse
Carry out acid anhydrides, as m ≠ n, which is blending type polyethylene maleic anhydride, i.e. polyethylene-Co- maleic anhydride；Work as m=n=1
When, which is alternate type polyethylene maleic anhydride, i.e. polyethylene-Alt- maleic anhydride.
2. the lithium ion anode water-based binder according to claim 1 containing pyridine groups, which is characterized in that the bonding
The molar content of pyridine groups is 10%~50% in agent side chain.
3. the lithium ion anode water-based binder according to claim 1 containing pyridine groups, which is characterized in that the bonding
Carboxylic acid is partial lithiation in agent side chain, that is, exists simultaneously carboxylic acid and carboxylic acid lithium.
4. the preparation method of the lithium ion anode water-based binder described in claim 1 containing pyridine groups, which is characterized in that packet
Containing following steps:
The polyethylene maleic anhydride and pyridinemethanol of certain mol proportion example are weighed, organic solvent is added and catalyst heat instead
It answers, the product that reaction obtains is added to stirring and dissolving in a certain amount of LiOH aqueous solution and carries out lithiumation, then in deionized water
Middle dialysis can be obtained binder after dry.
5. the preparation method of the lithium ion anode water-based binder according to claim 4 containing pyridine groups, feature exist
In the organic solvent is n,N-Dimethylformamide, and the catalyst is p-methyl benzenesulfonic acid.
6. a kind of lithium ion secondary battery, which is characterized in that the positive electrode of the lithium ion secondary battery by active material, lead
Binder composition prepared by electric material and claim 4.
7. lithium ion secondary battery according to claim 6, which is characterized in that the active material is LiFePO 4,
The conductive material is acetylene black.
8. lithium ion secondary battery according to claim 6, which is characterized in that the total mass fraction of the bonding agent is
3%~10%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697234A (en) * | 2020-06-19 | 2020-09-22 | 中国地质大学（武汉） | Water-based crosslinking binder for lithium ion battery and preparation method and application thereof |
| CN114361456A (en) * | 2022-01-11 | 2022-04-15 | 中国科学院化学研究所 | Water-based functional ion-conducting binder for lithium battery, preparation method and application |
| CN116179090A (en) * | 2022-11-16 | 2023-05-30 | 深圳市东升塑胶制品有限公司 | Ultrathin single-sided hot melt adhesive tape applied to lithium battery |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007091517A1 (en) * | 2006-02-07 | 2007-08-16 | Daikin Industries, Ltd. | Fluorine-containing polymer containing heteroaromatic ring |
| US7381260B2 (en) * | 2006-04-28 | 2008-06-03 | Toyo Ink Mfg. Co., Ltd. | Thiazineindigo pigment dispersant, and pigment composition, colored composition and color filter, using the same |
| CN103819660A (en) * | 2014-02-26 | 2014-05-28 | 福建湄洲湾氯碱工业有限公司 | Method for preparing polyester polyol through in situ modification of epoxy plant oil |
| WO2016079919A1 (en) * | 2014-11-18 | 2016-05-26 | 国立大学法人東京大学 | Electrolyte solution |
| US20160226102A1 (en) * | 2015-02-03 | 2016-08-04 | Blue Current, Inc. | Functionalized fluoropolymers and electrolyte compositions |
| CN106299377A (en) * | 2016-10-12 | 2017-01-04 | 东莞塔菲尔新能源科技有限公司 | A kind of bonder for lithium ion batteries and use the lithium ion battery of this binding agent |
| EP2392603B1 (en) * | 2009-03-11 | 2017-07-26 | Nippon Soda Co., Ltd. | Epoxy resin composition, curing agent, and curing accelerator |
| US20180040898A1 (en) * | 2016-08-08 | 2018-02-08 | Samsung Electronics Co., Ltd. | Positive electrode for metal air battery, metal air battery including the same, and method of preparing the positive electrode for metal air battery |
| WO2018045443A1 (en) * | 2016-09-12 | 2018-03-15 | Braskem S.A. | Intelligent polymer compositions |
| CN109728305A (en) * | 2018-08-31 | 2019-05-07 | 郑州中科新兴产业技术研究院 | A kind of complex adhesive and preparation method thereof for silicon-carbon cathode material |
-
2019
- 2019-05-31 CN CN201910469552.XA patent/CN110323444B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007091517A1 (en) * | 2006-02-07 | 2007-08-16 | Daikin Industries, Ltd. | Fluorine-containing polymer containing heteroaromatic ring |
| US7381260B2 (en) * | 2006-04-28 | 2008-06-03 | Toyo Ink Mfg. Co., Ltd. | Thiazineindigo pigment dispersant, and pigment composition, colored composition and color filter, using the same |
| EP2392603B1 (en) * | 2009-03-11 | 2017-07-26 | Nippon Soda Co., Ltd. | Epoxy resin composition, curing agent, and curing accelerator |
| CN103819660A (en) * | 2014-02-26 | 2014-05-28 | 福建湄洲湾氯碱工业有限公司 | Method for preparing polyester polyol through in situ modification of epoxy plant oil |
| WO2016079919A1 (en) * | 2014-11-18 | 2016-05-26 | 国立大学法人東京大学 | Electrolyte solution |
| US20160226102A1 (en) * | 2015-02-03 | 2016-08-04 | Blue Current, Inc. | Functionalized fluoropolymers and electrolyte compositions |
| US20180040898A1 (en) * | 2016-08-08 | 2018-02-08 | Samsung Electronics Co., Ltd. | Positive electrode for metal air battery, metal air battery including the same, and method of preparing the positive electrode for metal air battery |
| WO2018045443A1 (en) * | 2016-09-12 | 2018-03-15 | Braskem S.A. | Intelligent polymer compositions |
| CN106299377A (en) * | 2016-10-12 | 2017-01-04 | 东莞塔菲尔新能源科技有限公司 | A kind of bonder for lithium ion batteries and use the lithium ion battery of this binding agent |
| CN109728305A (en) * | 2018-08-31 | 2019-05-07 | 郑州中科新兴产业技术研究院 | A kind of complex adhesive and preparation method thereof for silicon-carbon cathode material |
Non-Patent Citations (2)
| Title |
|---|
| MIN LING ET AL: "Multifunctional SA-PProDOT Binder for Lithium Ion Batteries", 《NANO LETTERS》 * |
| RUPESH ROHAN ET AL: "Low-cost and sustainable corn starch as a high-performance aqueous binder in silicon anodes via in situ cross-linking", 《JOURNAL OF POWER SOURCES》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697234A (en) * | 2020-06-19 | 2020-09-22 | 中国地质大学（武汉） | Water-based crosslinking binder for lithium ion battery and preparation method and application thereof |
| CN114361456A (en) * | 2022-01-11 | 2022-04-15 | 中国科学院化学研究所 | Water-based functional ion-conducting binder for lithium battery, preparation method and application |
| CN116179090A (en) * | 2022-11-16 | 2023-05-30 | 深圳市东升塑胶制品有限公司 | Ultrathin single-sided hot melt adhesive tape applied to lithium battery |
| CN116179090B (en) * | 2022-11-16 | 2024-02-09 | 深圳市东升塑胶制品有限公司 | Ultrathin single-sided hot melt adhesive tape applied to lithium battery |
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