CN103872329A - Lithium ion secondary battery and negative electrode piece of lithium ion secondary battery - Google Patents
Lithium ion secondary battery and negative electrode piece of lithium ion secondary battery Download PDFInfo
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- CN103872329A CN103872329A CN201410099501.XA CN201410099501A CN103872329A CN 103872329 A CN103872329 A CN 103872329A CN 201410099501 A CN201410099501 A CN 201410099501A CN 103872329 A CN103872329 A CN 103872329A
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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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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a lithium ion secondary battery using a water-soluble adhesive and a negative electrode piece of the lithium ion secondary battery. The water-soluble adhesive is a modified polyacrylic acid polymer and is prepared by polymerizing monomers from 1 to 3 shown in the description or monomers 1 and 3 shown in the description through a free radical polymerization initiator. Compared with the prior art, the lithium ion secondary battery disclosed by the invention has the advantages that the adhesive can effectively improve the first-time charging and discharging efficiency of the lithium ion secondary battery, and the high-temperature circulation performance, the high-temperature storage performance and the charging and discharging ratio performance are greatly improved.
Description
Technical field
The invention belongs to field of lithium ion secondary, more particularly, the present invention relates to a kind of silicon stannum alloy class lithium rechargeable battery and negative plate thereof with better high temperature and cycle performance compared with high charge-discharge magnification performance that have.
Background technology
Lithium rechargeable battery, because having higher voltage and energy density, has obtained application widely in portable type electronic product.But the pocketing of electronic product and multifunction development, also have higher requirement to the energy density of lithium rechargeable battery.
At present, the negative material that lithium rechargeable battery is most widely used is graphite-like material with carbon element, but its capacity has approached theoretical value 376mAh/g, that is to say, even material with carbon element is improved, energy density is also difficult to further improve.In recent years, the alloy material such as silicon and tin (theoretical specific capacity is up to 4200mAh/g) that has a very high theoretical specific capacity becomes the research emphasis of ion secondary battery cathode material lithium gradually.But can there is larger change in volume (approximately 400%) in this type of alloy material, cause active material in battery charging and discharging cyclic process to be easy to progressively come off from collection liquid surface in lithium rechargeable battery charge and discharge process, causes battery capacity sharp-decay.
On the other hand, polyacrylic acid (PAA), because have good adhesive property, has been used as the bonding agent of lithium ion secondary battery negative pole alloy material.But, owing to there being free hydroxy-acid group in polyacrylic acid, battery in first charge and discharge process, need to consume a large amount of lithium ions come in and carboxylate radical, therefore there will be larger irreversible capacity loss; And, due to the thermal stability of free carboxylate radical a little less than, at high temperature can there is irreversible glutamic acid reaction and lose cementability in it, thereby greatly reduce the high-temperature behavior of battery.In addition, according to research, the decomposition that the acidity of polyacrylic acid itself also can catalytic electrolysis liquid, and then cause the problems such as cycle performance of battery variation, flatulence.
For above-mentioned technical problem, people in the industry has proposed multiple solution, but all there is the shortcoming that is difficult to make up in every kind of scheme, for example: 1) someone proposes with the free carboxylic acid group in lithium hydroxide and in polyacrylic acid, thus reach the object that reduces irreversible capacity loss in lithium rechargeable battery first charge-discharge process; But the hydrophily of the lithium salts PAALi that neutralization reaction generates is higher, cause the pole piece making to be difficult to by finish-drying, the crystallization water residual in pole piece can cause very large infringement to the cycle performance of battery; 2) someone polyacrylic acid analog copolymer after proposing to be modified by polyvinyl alcohol using carboxylic acid group is as the bonding agent of ion secondary battery cathode material lithium; But in the time using it in silicon stannum alloy class negative material battery, in order to reach good adhesive effect, the consumption of this type of bonding agent is often larger, this can cause the reduction of energy content of battery density undoubtedly; And the polyacrylic acid analog copolymer after modification has the weak lithium ion performance of leading, and can cause that the internal resistance of cell increases and causes battery efficiency and high rate performance to reduce; 3) somebody proposes, by by the monomer copolymerization of the strong polar functional group such as acrylic ester monomer and nitrile group-containing, to obtain and have the very LA class bonding agent of high adhesiveness energy; But this type of bonding agent is because containing strong polar functional group, the wettability that causes itself and common carbonates electrolyte a little less than, if so that can not jointly use with suitable electrolyte, just easily there are very serious polarization phenomena in battery; In addition, present inventor also finds, often there is the phenomenon that pole piece comes off in the pole piece that uses LA bonding agent to make, when in the time using together with negative material that in alloy type charge and discharge process, change in volume is larger, easily reduces the cycle performance of battery because of coming off of active material.
Summary of the invention
The object of the invention is to: provide a kind of because using novel binders to have compared with lithium rechargeable battery and the negative plate thereof of high charge-discharge magnification performance and first charge-discharge efficiency, better high temperature cyclic performance and high-temperature storage performance.
In order to realize foregoing invention object, the invention provides a kind of lithium ion secondary battery negative pole sheet, it comprises negative current collector and is coated in the cathode membrane on negative current collector, described cathode membrane comprises negative electrode active material, conductive agent and water soluble adhesive, described water soluble adhesive is modified polyacrylic acid base polymer
It is prepared from by radical polymerization initiator polymerization by monomer 1 and 3:
The molecular formula of monomer 1 is formula (1), and R1 is wherein selected from hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms; R2 be selected from have 1～12 carbon atom alkyl, there is any one in the aromatic radical of 6～14 carbon atoms; The mole percent that monomer 1 accounts for polymerization precursor (polymerization precursor herein refers to the monomer of participation polymerization reaction and the initator that reaction is used, and for example, polymerization precursor herein refers to monomer 1, monomer 3 and initator) is 60%～90%;
The molecular formula of monomer 3 is formula (3), R5 is wherein selected from hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms, n is the arbitrary integer between 0～20, X is O or NY, and the Y in NY is hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms; The mole percent that monomer 3 accounts for polymerization precursor is 0.1%～15%.
The present invention adopts to be had height and leads the hydroxy-acid group in the water-soluble polymers decorated polyacrylic acid of lithium ion, makes Novel polypropylene acids polymer after the modification bonding agent as ion secondary battery cathode material lithium.This kind of bonding agent has good cementability, in side chain, contain a large amount of electronegative ethers, carbonyl, amido, these electronegativity groups of side chain can adsorb lithium ion and impel lithium ion to transmit between this type of functional group, thereby have improved the ionic nature of leading of polyacrylic polymer bonding agent; And the polyacrylic high polymer main chain of this type of bonding agent has formed space network structure by the two keys on side chain, can effectively suppress the volumetric expansion in alloy type negative material charge and discharge process, thereby improve the cycle performance of battery.Visible, bonding agent used in the present invention had both retained the high-adhesive-strength of polyacrylic polymer, again because of can not to battery, efficiency and high-temperature behavior do not cause damage first containing free carboxy acid's base; Height in its side chain leads the ether of lithium ion performance or amido and greatly reduces the polarization of inside battery, and the pliability of side chain has also made up pole piece that polyacrylic polymer causes too by force due to the rigidity problem such as become fragile to a certain extent.Therefore, use the bonding agent of above-mentioned bonding agent as lithium rechargeable battery alloy type negative material, can not only effectively improve the first charge-discharge efficiency of battery, and battery high-temperature cycle performance, high-temperature storage performance and charge-discharge magnification performance are had greatly and improved.
One as lithium ion secondary battery negative pole sheet of the present invention is improved, and the polymerization single polymerization monomer of described modified polyacrylic acid base polymer also comprises monomer 2,
The molecular formula of monomer 2 is formula (2), R3, R4 wherein be all selected from hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms, n is the arbitrary integer between 0～20, X is O or NY, and the Y in NY is hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms; The mole percent that monomer 2 accounts for polymerization precursor (polymerization precursor herein refers to monomer 1, monomer 2, monomer 3 and initator) is 0%～30%.The advantage of doing is like this: according to the difference of monomer 1 and monomer 3 structures, can regulate the adding of monomer 2 the collateralization degree of polymer after polymerization, and side chain contain-X-CH
2-CH
2unit has the lithium ion of leading performance, can be in the crosslinked group concentration of aggregation thing, and that improves polymer leads lithium ion performance.
Due to described modified polyacrylic acid base polymer be by monomer 1～3 or the mixture of monomer 1 and 3 under radical polymerization initiator effect, between in 10 to 150 degrees Celsius, have solvent to exist or condition of no solvent under, polymerization reaction take place and the netted modified polyacrylic acid base polymer that generates.Therefore, this binding agent have advantages of that preparation method is simple, in preparation process without using any organic solvent.
One as lithium ion secondary battery negative pole sheet of the present invention is improved, and described radical polymerization initiator comprises the one in following material: azo compound, as azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) etc.; Inorganic peroxide, as sodium peroxydisulfate, hydrogen peroxide etc.; Organic peroxide, as benzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP) etc.; Hydroperoxide; Peroxy dicarbonate; Peroxycarboxylic acid esters; Ketone peroxide etc.; Initiator amount is 0.1%～5% of monomer gross mass.
One as lithium ion secondary battery negative pole sheet of the present invention is improved, and the molecular weight of described modified polyacrylic acid base polymer is 50,000 to 2,000,000, and more excellent molecular weight ranges is between 100,000 to 500,000.Its reason is: when the molecular weight of this type of macromolecular compound is too low, adhesive strength can be a little less than, but also can be partially dissolved in electrolyte; But when molecular weight is too high, can in slurry preparation process, be difficult to be dispersed because solubility is too low.
Due to described modified polyacrylic acid family macromolecule compound have well water-soluble, therefore can be directly that they are soluble in water, prepare slurry together with active material, conductive agent; Slurry is applied on collector, and dry rear coiling prepared negative plate.The percentage that described modified polyacrylic acid base polymer accounts for negative electrode active material total weight is 1%～10%, and more excellent ratio is 1% to 3%.This is that ratio is too high can be had a significant impact the energy density of battery because the too low meeting of bonding agent ratio cannot provide good adhesive effect.
One as lithium ion secondary battery negative pole sheet of the present invention is improved, and described negative electrode active material is selected from any one in following material: Si simple substance; Sn simple substance; SiO
x, 0<x<2; SnO
y, 0<y<2; The alloy material of at least one element in Si and Ti, Fe, Co, Ni, Cu.
One as lithium ion secondary battery negative pole sheet of the present invention is improved, and described alloy material comprises TiSi
2phase and Si phase.
One as lithium ion secondary battery negative pole sheet of the present invention is improved, and described conductive agent comprises any one or a few in following material: graphite, and as native graphite, Delanium etc.; Acetylene black, as Ketjen black etc.; Conductive fiber, as carbon fiber and metallic fiber etc.; Metal dust, as copper powder and nickel powder; Organic conductive polymer is as polyphenylene derivative etc.Above-mentioned conductive agent can use separately or multiple being combined with, and consumption is preferably and accounts for 1% to 5% of negative electrode active material gross mass.
One as lithium ion secondary battery negative pole sheet of the present invention is improved, and described negative current collector material is selected from stainless steel, nickel, copper, titanium, carbon, electroconductive resin, or is coated with copper sheet or the stainless steel substrates of nickel or titanium.
In order to realize foregoing invention object, the present invention also provides a kind of lithium rechargeable battery, it comprises positive plate, negative plate, is interval in the barrier film between adjacent positive/negative plate, and electrolyte, and negative plate is wherein the negative plate described in above arbitrary paragraph.
One as lithium rechargeable battery of the present invention is improved, described positive plate selects layered metal oxide containing lithium as positive electrode active materials, include but not limited to following material: layered lithium metal oxides, as cobalt acid lithium (LCO), nickel-cobalt-manganese ternary material (NMC) etc.; Spinel structure lithium metal oxide, as LiMn2O4 (LiMn
2o
4) etc.; Lithium metal phosphates, as LiFePO4 (LFP) etc.; Lithium metal pentafluoride sulfate, as fluoridize cobaltous sulfate lithium (LiCoFSO
4) etc.; Lithium vanadium metal hydrochlorate, as vanadic acid nickel lithium (LiNiVO
4) etc.
Improve as the one of lithium rechargeable battery of the present invention, described positive plate aluminium or the aluminium foil that is coated with conductive carbon are as plus plate current-collecting body.
One as lithium rechargeable battery of the present invention is improved, described electrolyte comprises nonaqueous solvents and be dissolved in solute wherein, and wherein nonaqueous solvents includes but not limited to ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid Methylethyl ester and their mixture; Solute includes but not limited to LiPF
6, LiBF
4, LiCl, LiAlCl
4, LiSbF
6, LiSCN, LiCl, LiCF
3sO
3, LiCF
3cO
2, LiN (CF
3sO
2), LiAsF
6, LiBC
4o
8.
Compared with prior art, the bonding agent that lithium rechargeable battery of the present invention and negative plate thereof adopt comprises and has the polyacrylic high polymer main chain of good bonding ability and have the side chain of well leading lithium ion performance, therefore effectively solved silicon stannum alloy class negative material and embedded/deviate from lithium ion the electrode active material that in process, change in volume occurs and cause and separate with collector, also solved and used lithium rechargeable battery charge-discharge magnification and the cycle performance that common electric insulation bonding agent causes to reduce problem.In addition, for plain polypropylene acid bonding agent, modified polypropene acids bonding agent used in the present invention has good thermal stability and chemical inertness, therefore can effectively solve the problems such as battery high-temperature behavior deterioration; And this type of bonding agent also has water-soluble preferably, can prepare negative plate without the need for machine solvent as dispersant, thereby reduce production cost and environmental pollution.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, lithium rechargeable battery of the present invention, negative plate and beneficial effect thereof are elaborated.
Fig. 1 is the cathode membrane microstructure schematic diagram of lithium rechargeable battery of the present invention.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and useful technique effect more clear, below in conjunction with embodiment, the present invention is further elaborated.Should be understood that, the embodiment describing in this specification is only used to explain the present invention, is not intended to limit the present invention, and formula, the ratio etc. of embodiment can be suited measures to local conditions to make a choice and result be there is no to substantial effect.
Refer to Fig. 1, the cathode membrane of lithium rechargeable battery of the present invention comprises negative electrode active material 10, conductive agent 20 and modified polyacrylic acid base polymer 30.Wherein, the unit of modified polyacrylic acid base polymer 30 has conduction ether (amine) base side chain 32.
Embodiment 1
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, butyl acrylate 364g, methoxypolyethylene glycol acrylate (weight average molecular weight 480) 150g, polyethyleneglycol diacrylate (weight average molecular weight 600) 2g are added in flask; Azodiisobutyronitrile (AIBN) 0.2g is dissolved in deionized water 900g, adds in above-mentioned flask, simultaneously by the acrylic acid content of gas chromatographic detection; Polymerization reaction carries out, after 20 hours, isolating polymer by decantation at 50 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 100 ℃, obtains 280 grams of polymer.The number-average molecular weight that records this polymer is 150,000, and the coefficient of dispersion is 1.6.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:3:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery A with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 2
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, methyl acrylate 56g, methoxypolyethylene glycol methacrylate (weight average molecular weight 480) 108g, polyethylene glycol dimethacrylate (weight average molecular weight 600) 36g are added in flask; Benzoyl peroxide (BPO) 20g is dissolved in DMF (1000g), adds in above-mentioned flask, simultaneously by the content of gas chromatographic detection methyl acrylate; Polymerization reaction carries out, after 16 hours, isolating polymer by decantation at 100 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 100 ℃, obtains 196 grams of polymer.The number-average molecular weight that records this polymer is 350,000, and the coefficient of dispersion is 1.5.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery B with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 3
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, methyl methacrylate 67g, polyethyene diamine DMAA (weight average molecular weight 500) 37g are added in flask; 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) 1g is dissolved in DMF1000g, adds in above-mentioned flask, simultaneously by the content of gas chromatographic detection methyl methacrylate; Polymerization reaction carries out, after 40 hours, isolating polymer by decantation at 70 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 80 ℃, obtains 82 grams of polymer.The number-average molecular weight that records this polymer is 500,000, and the coefficient of dispersion is 1.7.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery C with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 4
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, phenyl acrylate 191g, polyethyene diamine methyl ether Methacrylamide (weight average molecular weight 600) 164g, polyethyene diamine dimethylacrylate (weight average molecular weight 550) 1g are added in flask; Di-tert-butyl peroxide (DTBP) 13g is dissolved in DMF1000g, adds in above-mentioned flask, simultaneously by the content of gas chromatographic detection methyl methacrylate; Polymerization reaction carries out, after 40 hours, isolating polymer by decantation at 70 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 80 ℃, obtains 220 grams of polymer.The number-average molecular weight that records this polymer is 250,000, and the coefficient of dispersion is 1.3.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery D with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 5
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, methyl acrylate 12g, methoxypolyethylene glycol acrylate (weight average molecular weight 800) 62g, polyethylene glycol dimethacrylate (weight average molecular weight 1000) 26g are added in flask; Hydrogen peroxide 1g is dissolved in DMF1000g, adds in above-mentioned flask, simultaneously by the content of gas chromatographic detection methyl methacrylate; Polymerization reaction carries out, after 40 hours, isolating polymer by decantation at 60 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 80 ℃, obtains 80 grams of polymer.The number-average molecular weight that records this polymer is 200,000, and the coefficient of dispersion is 1.1.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery E with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 6
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, methyl methacrylate 85g, methoxypolyethylene glycol methacrylate (weight average molecular weight 750) 260g, polyethyleneglycol diacrylate (weight average molecular weight 650) 45g are added in flask; Azodiisobutyronitrile 12g is dissolved in DMF1000g, adds in above-mentioned flask, simultaneously by the content of gas chromatographic detection methyl methacrylate; Polymerization reaction carries out, after 40 hours, isolating polymer by decantation at 60 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 80 ℃, obtains 80 grams of polymer.The number-average molecular weight that records this polymer is 300,000, and the coefficient of dispersion is 1.2.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery F with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 7
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, butylacrylic acid methyl esters 121g and polyethyene diamine diacrylamine (weight average molecular weight 600) 90g are added in flask; Azodiisobutyronitrile 4g is dissolved in DMF1000g, adds in above-mentioned flask, simultaneously by the content of gas chromatographic detection butylacrylic acid methyl esters; Polymerization reaction carries out, after 10 hours, isolating polymer by decantation at 60 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 80 ℃, obtains 150 grams of polymer.The number-average molecular weight that records this polymer is 50,000, and the coefficient of dispersion is 1.1.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery G with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 8
The preparation of bonding agent: the air in three mouthfuls of glass flask that are 2L by internal volume with nitrogen replacement after, ethyl propylene heptyl heptylate 174g and polyethyene diamine diacrylamine (weight average molecular weight 600) 72g are added in flask; Azodiisobutyronitrile 2.4g is dissolved in DMF1000g, adds in above-mentioned flask, simultaneously by the content of gas chromatographic detection methyl methacrylate; Polymerization reaction carries out, after 60 hours, isolating polymer by decantation at 60 ℃, vacuumize at normal temperatures 24 hours, and then vacuumize 10 hours at 80 ℃, obtains 210 grams of polymer.The number-average molecular weight that records this polymer is 2000,000, and the coefficient of dispersion is 1.3.
The preparation of negative plate: the polymer of above-mentioned preparation is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polymer, acetylene black is 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery H with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Comparative example 1
The preparation of negative plate: polyacrylic acid (PAA) is dissolved in deionized water, add and be used as the Si powder that is coated with carbon of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Si powder, polyacrylic acid, acetylene black is 100:3:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, dry removal after solvent, cuts and makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery I with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Embodiment 9
The preparation of negative plate: the polymer of preparation in embodiment 1 is dissolved in deionized water, adds the SiO as negative active core-shell material
xacetylene black with as conductive agent, is fully mixed with cathode size, wherein SiO
x, polymer, acetylene black mass ratio be 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery J with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Comparative example 2
The preparation of negative plate: polyacrylic acid (PAA) is dissolved in deionized water, adds the SiO as negative active core-shell material
xacetylene black with as conductive agent, is fully mixed with cathode size, wherein SiO
x, polyacrylic acid, acetylene black mass ratio be 100:2:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery K with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Below data illustrate lithium ion secondary battery negative pole sheet of the present invention and use the various performances of the lithium rechargeable battery of this negative plate by experiment.
The preparation of negative plate: the polymer of preparation in embodiment 2 is dissolved in deionized water, add and be used as the Sn of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Sn, polymer, acetylene black is 100:1:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery L with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
Comparative example 3
The preparation of negative plate: polyacrylic acid (PAA) is dissolved in deionized water, add and be used as the Sn of negative active core-shell material and the acetylene black as conductive agent, fully be mixed with cathode size, wherein the mass ratio of Sn, polyacrylic acid, acetylene black is 100:1:5; The cathode size making is coated on to the Copper Foil both sides of 12 micron thickness, and 10h removal solvent is processed in forced air drying at 60 ℃, after cutting, makes negative plate.
The preparation of lithium rechargeable battery: use above-mentioned negative plate, with cobalt acid lithium (LiCoO
2) as positive plate, LiPF
6using the formulated solution of the mass ratio of 8:92 as electrolyte, be assembled into lithium rechargeable battery M with solvent (ethylene carbonate/diethyl carbonate/Methylethyl carbonic ester/ethenylidene carbonic ester mass ratio is 8/85/5/2).
High-temperature storage performance
At 25 ℃ take the electric current of 200mA to each battery charging until voltage as 4.2V; Battery after charging after standing 24 hours, is measured to the thickness recruitment of battery after placing at 85 ℃, account for the percentage of placing front cell thickness as thickness increment rate using thickness recruitment; Measure the volume recruitment of battery after placing, account for the percentage of placing front battery volume as volume increment rate using volume recruitment; The measurement result of each Battery pack is as shown in table 1.
Table 1, high-temperature storage performance test result
As can be seen from Table 1, due to PAA self weak thermal stability and acidity, use PAA, as battery I, the K of bonding agent and M, serious flatulence problem has at high temperature occurred and cause volume and thickness increment rate higher, all do not observe obvious high temperature flatulence phenomenon containing the polymer of esterification or amidatioon acrylic acid units as battery A-G, H, J and the L of bonding agent and only use.In this explanation PAA, free carboxylic acid group is the basic reason of flatulence problem, and modified polyacrylic acid base polymer used in the present invention can overcome this problem.Battery G and battery H do not have obvious flatulence phenomenon, but due to the bounce-back of pole piece thickness, after circulation, cell integrated thickness and volume still have larger increase.This may be therewith the two Battery packs polyacrylic bonding agents that use about the polyacrylic bonding agent molecular weight too low (50000) using in battery G, after can causing circulating because the adhesive strength of bonding agent own is excessively poor, battery has larger volume bounce-back; The polyacrylic bonding agent molecular weight too high (2000000) using in battery H, because bonding agent molecular weight is too high, in solvent, solubility is limited, causes it in pole piece manufacturing process, can not well be disperseed, and its cementability can not be brought into play.
First charge-discharge efficiency
Table 2, first charge-discharge efficiency test result
At 25 ℃ take the electric current of 200mA to each battery charging until voltage as 4.2V, to the battery after charging with the current discharge of 200mA until 2.5V; Measure charging capacity and the discharge capacity of battery, the first charge-discharge efficiency using the percentage of discharge capacity of the cell and charging capacity as battery; The measurement result of each Battery pack is as shown in table 2.
As can be seen from Table 2, due to the existence of free carboxylic acid group in PAA, use it all lower as battery I, the K of bonding agent and the first charge-discharge efficiency of M, this is because the free carboxy acid's base in PAA has irreversibly been caught part lithium ion in first charge-discharge process; But when in used bonding agent during only containing esterification or amidatioon acrylic acid units, battery A-G, H, J and L all have higher first charge-discharge efficiency, the first charge-discharge efficiency that acrylic-based adhesives esterification or amidatioon can effectively be improved to battery is described.
High-rate charge-discharge capability
At 25 ℃ take the electric current of 500mA to each battery charging until voltage as 4.2V, to the battery after charging with the current discharge of 500mA until 2.5V; Measure charging capacity and the discharge capacity of battery, the percentage of discharge capacity when battery discharges and recharges with the electric current of 200mA during with the discharge capacity of battery under this charging and discharging currents and 25 ℃, as the high-multiplying power discharge Capacity Ratio of battery; The measurement result of each Battery pack is as shown in table 3.
Table 3, high-rate charge-discharge capability test result
As can be seen from Table 3, battery I, the K and the M that make using PAA as bonding agent only can bring into play lower capacity under high current charge-discharge; And battery A-G, H, J and L that the polymer side chain of well leading lithium ion performance to contain ethers or amine tool is made as bonding agent discharge capacity under large electric current does not have too large reduction.This proves that modified polyacrylic acid base polymer used in the present invention can significantly improve the high rate performance of lithium rechargeable battery.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition,, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a lithium ion secondary battery negative pole sheet, it comprises negative current collector and is coated in the cathode membrane on negative current collector, described cathode membrane comprises negative electrode active material, conductive agent and water soluble adhesive, it is characterized in that: described water soluble adhesive is modified polyacrylic acid base polymer, it is prepared from by radical polymerization initiator polymerization by monomer 1 and 3:
The molecular formula of monomer 1 is formula (1), and R1 is wherein selected from hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms; R2 be selected from have 1～12 carbon atom alkyl, there is any one in the aromatic radical of 6～14 carbon atoms; The mole percent that monomer 1 accounts for polymerization precursor is 60%～90%;
The molecular formula of monomer 3 is formula (3), R5 is wherein selected from hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms, n is the arbitrary integer between 0～20, X is O or NY, and the Y in NY is hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms; The mole percent that monomer 3 accounts for polymerization precursor is 0.1%～15%;
Described polymerization precursor refers to participate in the monomer of polymerization reaction and the initator that reaction is used.
2. lithium ion secondary battery negative pole sheet according to claim 1, is characterized in that: the polymerization single polymerization monomer of described modified polyacrylic acid base polymer also comprises monomer 2,
The molecular formula of monomer 2 is formula (2), R3, R4 wherein be all selected from hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms, n is the arbitrary integer between 0～20, X is O or NY, and the Y in NY is hydrogen atom, have the alkyl of 1～12 carbon atom, have any one in the aromatic radical of 6～14 carbon atoms; The mole percent that monomer 2 accounts for polymerization precursor is 0%～30%.
3. lithium ion secondary battery negative pole sheet according to claim 2, it is characterized in that: described water soluble adhesive be by monomer 1～3 or monomer 1 and 3 under radical polymerization initiator effect, between in 10 to 150 degrees Celsius, have solvent to exist or condition of no solvent under, polymerization reaction take place and the netted modified polyacrylic acid base polymer that generates.
4. lithium ion secondary battery negative pole sheet according to claim 3, it is characterized in that: described radical polymerization initiator comprises the one in azo compound, inorganic peroxide, organic peroxide, hydroperoxide, peroxy dicarbonate, peroxycarboxylic acid esters, ketone peroxide, initiator amount is 0.1%～5% of polymerization precursor.
5. lithium ion secondary battery negative pole sheet according to claim 1, is characterized in that: the molecular weight of described modified polyacrylic acid base polymer is 20,000 to 2,000,000, and more excellent molecular weight ranges is between 100,000 to 500,000.
6. lithium ion secondary battery negative pole sheet according to claim 1, is characterized in that: the percentage that described modified polyacrylic acid base polymer accounts for negative electrode active material total weight is 1%～10%, and more excellent ratio is 1% to 3%.
7. lithium ion secondary battery negative pole sheet according to claim 1, is characterized in that: described negative electrode active material is selected from any one in following material: Si simple substance; Sn simple substance; SiO
x, 0<x<2; SnO
y, 0<y<2; The alloy material of at least one element in Si and Ti, Fe, Co, Ni, Cu.
8. lithium ion secondary battery negative pole sheet according to claim 7, is characterized in that: described alloy material comprises TiSi
2phase and Si phase.
9. lithium ion secondary battery negative pole sheet according to claim 1, is characterized in that: described conductive agent is selected from graphite, acetylene black, conductive fiber, metal dust and organic conductive polymer; Described negative current collector material is selected from stainless steel, nickel, copper, titanium, carbon, electroconductive resin, or is coated with copper sheet or the stainless steel substrates of nickel or titanium.
10. a lithium rechargeable battery, comprises positive plate, negative plate, is interval in the barrier film between adjacent positive/negative plate, and electrolyte, it is characterized in that: described negative plate is the negative plate described in any one in claim 1 to 9; Described positive plate selects layered metal oxide containing lithium as positive electrode active materials, and aluminium or the aluminium foil that is coated with conductive carbon are as plus plate current-collecting body; Described electrolyte comprises nonaqueous solvents and be dissolved in solute wherein, and wherein, nonaqueous solvents comprises one or more in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid Methylethyl ester, and solute comprises LiPF
6, LiBF
4, LiCl, LiAlCl
4, LiSbF
6, LiSCN, LiCF
3sO
3, LiCF
3cO
2, LiN (CF
3sO
2), LiAsF
6, LiBC
4o
8in one or more.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356979A (en) * | 2014-10-28 | 2015-02-18 | 深圳市贝特瑞新能源材料股份有限公司 | Polyacrylate water-based adhesive for electrode materials of lithium ion battery, preparation method of adhesive and electrode plates of lithium ion battery |
| CN109309230A (en) * | 2017-07-28 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Secondary battery pole piece, preparation method thereof and secondary battery using pole piece |
| CN109755580A (en) * | 2018-12-29 | 2019-05-14 | 桑德集团有限公司 | A kind of lithium-sulfur cell binder and preparation method thereof, positive electrode |
| CN110313089A (en) * | 2017-03-31 | 2019-10-08 | 松下电器产业株式会社 | Anode for nonaqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| CN112909251A (en) * | 2019-12-04 | 2021-06-04 | 广州汽车集团股份有限公司 | Negative electrode material active layer, negative electrode pole piece, lithium ion cell, lithium ion battery pack and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101138629B1 (en) * | 2009-08-14 | 2012-04-26 | 주식회사 엘지화학 | Binder for Secondary Battery Exhibiting Excellent Adhesive Force |
| CN103500835A (en) * | 2013-10-10 | 2014-01-08 | 东莞新能源科技有限公司 | Lithium ion secondary battery and negative piece thereof |
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2014
- 2014-03-18 CN CN201410099501.XA patent/CN103872329B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356979A (en) * | 2014-10-28 | 2015-02-18 | 深圳市贝特瑞新能源材料股份有限公司 | Polyacrylate water-based adhesive for electrode materials of lithium ion battery, preparation method of adhesive and electrode plates of lithium ion battery |
| CN104356979B (en) * | 2014-10-28 | 2017-02-15 | 深圳市贝特瑞新能源材料股份有限公司 | Polyacrylate water-based adhesive for electrode materials of lithium ion battery, preparation method of adhesive and electrode plates of lithium ion battery |
| CN110313089A (en) * | 2017-03-31 | 2019-10-08 | 松下电器产业株式会社 | Anode for nonaqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| CN109309230A (en) * | 2017-07-28 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Secondary battery pole piece, preparation method thereof and secondary battery using pole piece |
| CN109309230B (en) * | 2017-07-28 | 2021-11-02 | 宁德时代新能源科技股份有限公司 | Secondary battery pole piece, preparation method thereof and secondary battery using pole piece |
| CN109755580A (en) * | 2018-12-29 | 2019-05-14 | 桑德集团有限公司 | A kind of lithium-sulfur cell binder and preparation method thereof, positive electrode |
| CN112909251A (en) * | 2019-12-04 | 2021-06-04 | 广州汽车集团股份有限公司 | Negative electrode material active layer, negative electrode pole piece, lithium ion cell, lithium ion battery pack and application thereof |
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