CN101662026A - Bonder composition, compositions of anode and cathode materials, anode, cathode and battery - Google Patents
Bonder composition, compositions of anode and cathode materials, anode, cathode and battery Download PDFInfo
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- CN101662026A CN101662026A CN200810210167A CN200810210167A CN101662026A CN 101662026 A CN101662026 A CN 101662026A CN 200810210167 A CN200810210167 A CN 200810210167A CN 200810210167 A CN200810210167 A CN 200810210167A CN 101662026 A CN101662026 A CN 101662026A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a bonder composition which contains a first bonder and a second bonder, wherein the curing temperature of the first bonder is higher than 150 to 500 DEG C, and the curing temperature of the second bonder is 50-150 DEG C. The invention also provides an anode material composition, an anode, a cathode material composition, a cathode and a lithium ion secondary battery. The lithium ion secondary battery comprises a battery shell, an electrode core and an electrolyte, wherein the electrode core and the electrolyte are sealed and accommodated in the battery shell; the electrode core comprises the anode, the cathode and a diaphragm between the anode and the cathode; and the anode and/or the cathode are/is provided by the invention. The battery containing the bonder composition has higher capacity and cycle performance.
Description
Technical field
The present invention relates to a kind of adhesive composition, comprise this adhesive composition the positive electrode composition, comprise this adhesive composition the negative material composition, comprise the positive electrode composition positive pole, comprise the negative pole of negative material composition and the battery that comprises described positive pole and/or negative pole.
Background technology
In recent years, the high speed development of electronic technology alleviates electronics miniaturization and quality, thereby increasing portable electric appts occurred.Lithium rechargeable battery is with its discharge voltage height, energy density height and recycle the first-selected energy that long advantage of life-span becomes these portable electric appts.
The performance of lithium rechargeable battery is subjected to the influence of many factors, as the character of positive electrode active materials, character, conductive agent, electrolyte, barrier film and the binding agent of negative active core-shell material.For example, the LiFePO4 as positive electrode active materials has good thermal stability and security performance; LiFePO4 aboundresources, low price, environmentally safe are a kind of very potential anode material for lithium-ion batteries.But, the LiFePO4 specific area is big, need more binding agent when making lithium ion cell positive, and LiFePO 4 material density is low, the positive plate fragility of load LiFePO 4 material is big, and it is lower to add the pressure that can bear man-hour, therefore, contact defective tightness between the LiFePO4 particle, the maximum compacted density of LiFePO 4 material is 2.2g/cm
3About, therefore the capacitance of the battery made from this class positive active material is lower, and cycle performance is also not ideal enough.
Along with the continuous development of lithium rechargeable battery, a lot of new materials constantly are applied in the lithium rechargeable battery, particularly negative electrode active material.In the research of anticathode active material, the most active to the research of Si and Sn.Si and Sn etc. can form alloy with lithium as lithium ion battery negative material, have high specific capacity.The theoretical capacity of Sn is 900mAh/g, and the theoretical capacity of Si is then up to 4200mAh/g.But silicon, tin are taking off/the huge change in volume of embedding lithium front and back meeting generation, and volumetric expansion is about 4 times behind the complete embedding lithium of silicon.Violent change in volume like this has caused a series of problems in the charge and discharge process, thereby causes losing the removal lithium embedded ability such as fragmentation, the efflorescence of active material particle in the cyclic process.Therefore, during as negative electrode active material, have higher initial capacity, but cycle performance is relatively poor with Si and Sn.
Summary of the invention
The objective of the invention is the defective of and/or cycle performance difference low, a kind of adhesive composition that can improve battery capacity and/or cycle performance is provided for the capacity that overcomes the lithium rechargeable battery that prior art provides.
The invention provides a kind of adhesive composition, wherein, said composition contains first binding agent and second binding agent, wherein, said composition contains first binding agent and second binding agent, wherein, the curing temperature of described first binding agent is greater than 150 ℃ to 500 ℃, and the curing temperature of described second binding agent is 50-150 ℃.
The present invention also provides a kind of positive electrode composition, and said composition comprises positive active material, conductive agent and binding agent, and wherein, described binding agent is an adhesive composition provided by the invention.
The present invention also provides a kind of positive pole, and this positive pole comprises collector and the positive electrode that loads on the collector, and wherein, described positive electrode is a positive electrode composition provided by the invention.
The present invention also provides a kind of negative material composition, and said composition comprises negative electrode active material and binding agent, and wherein, described binding agent is an adhesive composition provided by the invention.
The present invention also provides a kind of negative pole of lithium rechargeable battery, and this negative pole comprises collector and the positive electrode that loads on the collector, and wherein, described negative material is a negative material composition provided by the invention.
The present invention also provides a kind of lithium rechargeable battery, this lithium rechargeable battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, described positive pole just very provided by the invention and/or described negative pole are negative pole provided by the invention.
The present inventor find when the binding agent in positive pole and/or the negative pole be contain curing temperature be greater than 150 ℃ when the binding agent more than 500 ℃ and curing temperature are 50-150 ℃ the composition of binding agent, can improve the density of positive pole and/or negative pole coating, and, have the capacity and/or the cycle performance of improvement by the battery of this positive pole and/or negative pole assembling.For example, the density of the anodal coating of embodiment 1 is 2.8 gram per centimeters
3, the 0.2C discharge capacity is 920 MAHs, cycle-index is 700 times; The anodal coating of the preparation of Comparative Examples 1 density be 2.28 gram per centimeters
3, the 0.2C discharge capacity is 700 MAHs, cycle-index is 630 times.When using silica flour or alloy silicon as negative electrode active material, can greatly improve cycle performance, drop to 80% of initial capacity as capacitance after battery B 1 circulation of embodiment 4 preparations 200 times; And the battery BB1 of Comparative Examples preparation 30 capacitances that only circulate just drop to 80% of initial capacity.
Embodiment
The invention provides a kind of adhesive composition, wherein, said composition contains first binding agent and second binding agent, wherein, said composition contains first binding agent and second binding agent, wherein, the curing temperature of described first binding agent is greater than 150 ℃ to 500 ℃, and the curing temperature of described second binding agent is 50-150 ℃.Described curing temperature is meant that a kind of binding agent is frozen into the temperature of the required arrival of solid.
In adhesive composition provided by the invention, as long as exist a spot of described first binding agent just can realize purpose of the present invention; A kind of preferred embodiment in, the weight ratio of described first binding agent and second binding agent is 1: 9 to 9: 1; For capacity and the cycle performance that further improves lithium rechargeable battery, in another preferred embodiment, the weight ratio of described first binding agent and second binding agent is 3: 7 to 7: 3.
Described first binding agent can be any binding agent greater than 150 ℃ to 500 ℃ for curing temperature, is preferably in polyimides (PI), epoxy resin, siloxane polymer, the phenolic resins one or more; Described second binding agent can be that curing temperature is any binding agent of 50-150 ℃, is preferably in sodium carboxymethylcellulose, butadiene-styrene rubber, polytetrafluoroethylene, polyvinyl alcohol, polyurethane, polyvinylidene fluoride, vinylidene fluoride-TFE copolymer, vinylidene difluoride-hexafluoropropylene copolymer, hexafluoropropylene-TFE copolymer, the vinylidene fluoride-tetrafluoraoethylene-hexafluoropropylene copolymer one or more.
The preparation of adhesive composition provided by the invention can for example place the blender mixing to get final product according to certain weight ratio first binding agent and second binding agent by the method preparation that mixes.
The present invention also provides a kind of positive electrode composition, and said composition comprises positive active material, conductive agent and binding agent, and wherein, described binding agent is an adhesive composition provided by the invention.
The content of described active material and conductive agent can be customary amount; Under the preferable case, for example, be benchmark with the total weight of positive active material, conductive agent and binding agent, the content of described binding agent can be 0.3-15 weight %, is preferably 1-13 weight %; The content of described positive active material can be 83-98 weight %, is preferably 85-95 weight %; The content of described conductive agent can be 1-10 weight %, is preferably 3-10 weight %.
Described positive active material can adopt the positive active material of various routines, as LiFePO4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F and LiFeO
2In one or more.In order significantly to improve described positive active material performance, described positive active material performance is preferably LiFePO4, LiCoO
2, LiVPO
4Among the F one or more.
Described conductive agent can adopt any conductive agent known in the field, for example can adopt in graphite, carbon fiber, carbon black, metal dust and the fiber one or more.These compounds can be by commercially available.
The present invention also provides a kind of positive pole, and this positive pole comprises collector and the positive electrode that loads on the collector, and wherein, described positive electrode is a positive electrode composition provided by the invention.
Described collector can adopt the various collectors that are used for lithium ion secondary battery positive electrode in the prior art, as aluminium foil, Copper Foil or various Punching steel strip.
Anodal preparation method can carry out in accordance with the following methods, with solvent positive active material, binding agent and conductive agent are prepared into the positive electrode slurries, the viscosity that the addition of solvent can be coated with according to the slurry of the anodal slurries that will prepare and the requirement of operability are adjusted flexibly, are specially known in those skilled in the art.Then prepared positive electrode slurries slurry being coated in drying on the plus plate current-collecting body, is to keep 0.5-5 hour down greater than 150 ℃ to 500 ℃ in temperature then, makes described first kind of adhesive cures.Then carry out compressing tablet and cut-parts and obtain positive pole.The temperature of described drying can be 80-150 ℃, and can be 2-10 hour drying time.
The used solvent of described anodal slurries can be an all kinds of solvents of the prior art, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of solvent can be coated on the described conducting base described slurry and gets final product.In general, it is 40-150 weight % that the consumption of solvent makes the content of positive active material in the slurries, is preferably 50-85 weight %.
The present invention also provides a kind of negative material composition, and said composition comprises negative electrode active material and binding agent, and wherein, described binding agent is an adhesive composition provided by the invention.
The content of described negative electrode active material can be the customary amount of this area, a kind of preferred embodiment in, total weight with described negative electrode active material and binding agent is a benchmark, and the content of described binding agent can be 0.3-20 weight %, is preferably 1-15 weight %; The content of described negative electrode active material is 80-99.7 weight %, is preferably 85-99 weight %.
Described negative electrode active material can adopt all negative electrode active materials that can be purchased, and is preferably in silicon materials, tin and the carbonaceous material one or more; Wherein, described silicon materials are pure silicon powder, alloy silicon; Described carbonaceous material comprises activated carbon, hard carbon and soft carbon.When negative electrode active material is silica flour and/or tin, adopt adhesive composition of the present invention can greatly improve the cycle performance of battery, so negative electrode active material especially is preferably silica flour and/or tin.
A kind of preferred embodiment in, negative material composition of the present invention also comprises conductive agent, described conductive agent can be the conductive agent of routine.The content of conductive agent can be customary amount, is preferably, and be benchmark with the total weight of negative electrode active material, conductive agent and binding agent, the content of described binding agent is 1-15 weight %; The content of described negative electrode active material is 85-95 weight %; The content of described conductive agent is 3-10 weight %.
The present invention also provides a kind of negative pole of lithium rechargeable battery, and this negative pole comprises collector and the positive electrode that loads on the collector, and wherein, described negative material is a negative material composition provided by the invention.
Described collector can be for negative current collector commonly used in the lithium ion battery, as stamped metal, metal forming, net metal and foamed metal.
The preparation method of described negative pole is similar with anodal preparation method, is not described in detail in this.
The present invention also provides a kind of lithium rechargeable battery, this lithium rechargeable battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, described positive pole just very provided by the invention and/or described negative pole are negative pole provided by the invention.
When battery provided by the invention just very provided by the invention anodal, its negative pole can be the negative pole of routine.The negative pole of described routine is meant that the binding agent that loads on the flow collection sheet is conventional binding agent, as in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) and the butadiene-styrene rubber (SBR) one or more; Its negative pole can also be negative pole provided by the invention, and this combination is most preferred.
When the negative pole of battery provided by the invention was negative pole provided by the invention, its positive pole can be the positive pole of routine.The positive pole of described routine is meant that the binding agent that loads on the flow collection sheet is conventional binding agent, as in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC) and the butadiene-styrene rubber (SBR) one or more.
In lithium rechargeable battery of the present invention, electrolyte can be nonaqueous electrolytic solution.Described nonaqueous electrolytic solution is the solution that electrolyte lithium salt forms in nonaqueous solvents, can use the nonaqueous electrolytic solution of routine well known by persons skilled in the art.Can be selected from lithium hexafluoro phosphate (LiPF as electrolyte lithium salt
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenyl lithium borate (LiB (C
6H
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based sulfonic acid lithium (LiC (SO
2CF
3)
3), LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Nonaqueous solvents can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain in the chain organosilane ester of unsaturated bond one or more.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain in the ring-type organosilane ester of unsaturated bond one or more for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
In lithium rechargeable battery of the present invention, membrane layer is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.Described membrane layer can be selected from and well known to a person skilled in the art various membrane layers used in the lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane (PP), polyethylene felt (PE), glass mat or ultra-fine fibre glass paper or PP/PE/PP.As preferred embodiment a kind of, described barrier film is a polyimide film.Any polyimide film that described polyimide film can adopt for this area, preferably its porosity is 20%-55%, average pore diameter is the 30-120 nanometer.
The preparation method of lithium rechargeable battery provided by the invention carries out according to method as well known to those skilled in the art, in general, this method comprises anodal, negative pole and the barrier film between positive pole and the negative pole formation pole piece of reeling successively, pole piece is inserted in the battery case, add electrolyte, sealing then, wherein, described positive pole comprises collector and the positive electrode that loads on the collector, described positive electrode contains positive active material, conductive agent and binding agent, wherein, described binding agent and/or described binding agent are adhesive composition provided by the invention.Wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is a conventional amount used.
Below be that example illustrates lithium rechargeable battery of the present invention with 053450 size battery.
Embodiment 1
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
The preparation of adhesive composition: is to mix at 3: 7 CMC and PI (it is 200-300 ℃ that Changzhou extensively becomes novel plastic Co., Ltd, curing temperature) according to weight ratio.
The positive electrode composition: with the adhesive composition of LiFePO4, acetylene black and above-mentioned preparation is to mix at 100: 5: 6 by weight.
Anodal: the positive electrode composition water of above-mentioned preparation is mixed well, and is two-sided dressing on 20 microns the aluminium foil at thickness, smears evenly.90 ℃ of oven dry down, solidified 3 hours down at 250 ℃ then.Roll, rolling cut becomes positive plate, and the pole piece size is 48.5cm (length) * 4.4cm (wide) * 0.015cm (thickness), contains 7 gram positive active materials.Calculate the density of anodal coating according to following formula:
Be coated with weight/(being coated with the volume of dressing on the pole piece) of dressing on density=pole piece
Result calculated is listed in the table 1.
Negative pole: is that 100: 4: 1.6 waters mix with Delanium, CMC and SBR according to weight ratio.Be two-sided dressing on 12 microns the Copper Foil at thickness, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes negative plate, and the pole piece size is 48cm (length) * 4.5cm (wide) * 0.01cm (thickness), and negative material graphite weighs 3 grams.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: the PE film that adopts 20 micron thickness.
With the lithium-ion electric core of an above-mentioned positive and negative plate and a square of membrane coil coiled and be received in the rectangular cell shell, inject 1 mol LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 1) electrolyte, the lithium ion battery C1 of 053450 type is made in sealing.
Comparative Examples 1
This Comparative Examples is used to illustrate lithium rechargeable battery that prior art provides and preparation method thereof.
The positive electrode composition: with LiFePO4, acetylene black and CMC is to mix at 100: 5: 6 by weight.
Anodal: water is mixed well the positive electrode composition of above-mentioned preparation.Be two-sided dressing on 20 microns the aluminium foil at thickness, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 48.5cm (length) * 4.4cm (wide) * 0.015cm (thickness), contains 5.5 gram positive active materials.
Calculate the density of anodal coating according to the formula among the embodiment 1, with the results are shown in the table 1 of detecting.
Negative pole: the method for preparing negative pole according to embodiment 1 carries out calculating according to the formula among the embodiment 1 density of negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: identical with embodiment 1.
Method assembled battery CC1 according to embodiment 1.
Embodiment 2
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
The preparation of adhesive composition: is to mix at 7: 3 polyvinylidene fluoride and phenolic resins (Tianjin be full of greatly resin Co., Ltd, curing temperature be 300-450 ℃) according to weight ratio.
The positive electrode composition: with LiFePO4, the adhesive composition of acetylene black and above-mentioned preparation is to mix at 100: 8: 12 by weight.
Anodal: with NMP the positive electrode composition of above-mentioned preparation being mixed well, is two-sided dressing on 20 microns the aluminium foil at thickness, smears evenly.90 ℃ of oven dry down, solidified 3 hours down at 400 ℃ then.Roll, rolling cut becomes positive plate, and the pole piece size is 48.5cm * 4.5cm * 0.015cm (thickness), and positive electrode weighs 7 grams.Calculate the density of anodal coating according to the formula among the embodiment 1, with the results are shown in the table 1 of detecting.
Negative pole: the method for preparing negative pole according to embodiment 1 is carried out.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: identical with embodiment 1.
Method assembled battery C2 according to embodiment 1.
Comparative Examples 2
This Comparative Examples is used to illustrate lithium rechargeable battery that prior art provides and preparation method thereof.
The positive electrode composition: with LiFePO4, acetylene black and polyvinylidene fluoride is to mix at 100: 8: 8 by weight.
Anodal: water is mixed well the positive electrode composition of above-mentioned preparation.Be two-sided dressing on 20 microns the aluminium foil at thickness, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 48.5cm (length) * 4.4cm (wide) * 0.015cm (thickness), contains 5.5 gram positive active materials.Calculate the density of anodal coating according to the formula among the embodiment 1, with the results are shown in the table 1 of detecting.
Negative pole: the method for preparing negative pole according to embodiment 2 is carried out.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: identical with embodiment 2.
Method assembled battery CC2 according to embodiment 2.
Embodiment 3
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
Adhesive composition 1: the method for preparing adhesive composition according to embodiment 1 is carried out.
Positive electrode composition: carry out according to embodiment 1 preparation positive electrode method for compositions.
Anodal: as to prepare anodal method according to embodiment 1 and carry out.
The preparation of adhesive composition 2: is mixing in 4: 6 with CMC and epoxy resin (Tao Shi (Zhangjiagang) chemical company, curing temperature are 150-200 ℃) according to weight ratio.
The negative material composition: with the adhesive composition of activated carbon and above-mentioned preparation is to mix at 100: 2: 2 by weight.
Negative pole: water is mixed well the negative material composition of above-mentioned preparation, is two-sided dressing on 12 microns the Copper Foil at thickness, smears evenly.90 ℃ of oven dry down, solidified 3 hours down at 160 ℃ then.Roll, rolling cut becomes negative plate, and the pole piece size is 48cm (length) * 4.5cm (wide) * 0.0093cm (thickness), and negative material graphite weighs 3 grams.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Identical with embodiment 1.
Method assembled battery C3 according to embodiment 1.
Embodiment 4
Present embodiment is used to illustrate lithium rechargeable battery provided by the invention and preparation method thereof.
Anodal: with LiCoO
2, acetylene black and PVDF be that 100: 5: 4 usefulness solvent NMP mix well by weight, mixes, and is two-sided dressing on 20 microns the aluminium foil at thickness, smear evenly.90 ℃ of oven dry down, roll, rolling cut becomes positive plate, and the pole piece size is 48.5cm (length) * 4.4cm (wide) * 0.015cm (thickness), contains 10 gram positive active materials.Calculate the density of anodal coating according to the formula among the embodiment 1, with the results are shown in the table 1 of detecting.
The preparation of adhesive composition: is 2: 8 mixing with PI (it is 200-300 ℃ that Changzhou extensively becomes novel plastic Co., Ltd, curing temperature) according to weight ratio with CMC.
The negative material composition: with the adhesive composition of pure silicon powder and above-mentioned preparation is to mix at 100: 10 by weight.
Negative pole: water is mixed well the negative material composition of above-mentioned preparation, is two-sided dressing on 12 microns the Copper Foil at thickness, smears evenly.90 ℃ of oven dry down, solidified 3 hours down at 250 ℃ then.Roll, rolling cut becomes positive plate, and the pole piece size is 48cm (length) * 4.5cm (wide) * 0.007cm (thickness), and negative material weighs 1.6 grams.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: the PE film that adopts 20 micron thickness.
With the lithium-ion electric core of an above-mentioned positive and negative plate and a square of membrane coil coiled and be received in the rectangular cell shell, inject 1 mol LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 1) electrolyte, the lithium ion battery B1 of 053450 type is made in sealing.
Comparative Examples 3
Anodal: as to prepare anodal method preparation according to embodiment 4.
The negative material composition: with pure silicon powder and CMC is to mix at 100: 10 by weight.
Negative pole: water is mixed well the negative material composition of above-mentioned preparation, is two-sided dressing on 12 microns the Copper Foil at thickness, smears evenly, 90 ℃ of oven dry down.Roll, rolling cut becomes negative plate, and the pole piece size is 48cm (length) * 4.5cm (wide) * 0.007cm (thickness), and negative material weighs 1.4 grams.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: identical with embodiment 4.
Method assembled battery BB1 according to embodiment 4.
Embodiment 5
Anodal: as to prepare anodal method according to embodiment 4 and carry out.
The preparation of adhesive composition: is to mix at 5: 5 CMC and phenolic resins (Tianjin be full of greatly resin Co., Ltd, curing temperature be 300-450 ℃) according to weight ratio.
The negative material composition: with the adhesive composition of alloy silicon and above-mentioned preparation is to mix at 100: 8 by weight.
Negative pole: water is mixed well the negative material composition of above-mentioned preparation, is two-sided dressing on 12 microns the Copper Foil at thickness, smears evenly.90 ℃ of oven dry down, solidified 3 hours down at 400 ℃ then.Roll, rolling cut becomes positive plate, and the pole piece size is 48cm (length) * 4.5cm (wide) * 0.007cm (thickness), and negative material weighs 1.6 grams.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: the PE film that adopts 20 micron thickness.
With the lithium-ion electric core of an above-mentioned positive and negative plate and a square of membrane coil coiled and be received in the rectangular cell shell, inject 1 mol LiPF subsequently
6/ (EC+DEC+DMC) (EC, DEC and DMC weight ratio are 1: 1: 1) electrolyte, the lithium ion battery B2 of 053450 type is made in sealing.
Comparative Examples 4
Anodal: as to prepare anodal method preparation according to embodiment 5.
The negative material composition: with alloy silicon and CMC is to mix at 100: 8 by weight.
Negative pole: water is mixed well the negative material composition of above-mentioned preparation, is two-sided dressing on 12 microns the Copper Foil at thickness, smears evenly, 90 ℃ of oven dry down.Roll, rolling cut becomes negative plate, and the pole piece size is 48cm (length) * 4.5cm (wide) * 0.007cm (thickness), and negative material weighs 1.4 grams.According to the density of the calculating of the formula among the embodiment 1 negative pole coating, with the results are shown in the table 1 of detecting.
Barrier film: identical with embodiment 5.
Method assembled battery BB2 according to embodiment 5.
Battery performance test
1, the test of capacity
Under A, the room temperature, the battery that embodiment 1-3 and Comparative Examples 1-2 are made is respectively with 1C current charges to 3.8 volt, and after voltage rose to 3.8 volts, with 3.8 volts of constant-potential charges, cut-off current was 0.05C, shelved 5 minutes; Then battery is lied prostrate with 0.2C current discharge to 2.4 respectively, obtain the capacity of battery normal temperature 0.2C current discharge to 2.4 volt; Repeat above-mentioned charge step then, and once more respectively with battery with the 2C current discharge, obtain the capacity of battery under the normal temperature with 2C current discharge to 2.4 volt.What record the results are shown in the table 1.
Under B, the room temperature, the battery that embodiment 4-5 and Comparative Examples 3-42 are made is respectively with 1C current charges to 4.2 volt, and after voltage rose to 4.2 volts, with 4.2 volts of constant-potential charges, cut-off current was 0.05C, shelved 5 minutes; Then battery is lied prostrate with 0.2C current discharge to 3.0 respectively, obtain the capacity of battery normal temperature 0.2C current discharge to 3.0 volt; Repeat above-mentioned charge step then, and once more respectively with battery with the 2C current discharge, obtain the capacity of battery under the normal temperature with 2C current discharge to 3.0 volt.What record the results are shown in the table 1.
2, the mensuration of cycle performance
A, under 45 ℃, the battery that embodiment 1-3 and Comparative Examples 1-2 are made lies prostrate with 1C current charges to 3.8 respectively, after voltage rises to 3.8 volts, with 3.2 volts of constant-potential charges, cut-off current is 0.05C, shelved 5 minutes, and then battery was lied prostrate with 1C current discharge to 2.4 respectively, write down the discharge capacity of each battery respectively; Repeat the above-mentioned step that discharges and recharges then.Described cycle-index is the number of times that capacitance drops to circulation in 80% o'clock of initial capacity, and what record the results are shown in the table 1.
B, under 45 ℃, the battery that embodiment 4-5 and Comparative Examples 3-4 are made lies prostrate with 1C current charges to 4.2 respectively, after voltage rises to 4.2 volts, with 4.2 volts of constant-potential charges, cut-off current is 0.05C, shelved 5 minutes, and then battery was lied prostrate with 1C current discharge to 3.0 respectively, write down the discharge capacity of each battery respectively; Repeat the above-mentioned step that discharges and recharges then.Described cycle-index is the number of times that capacitance drops to circulation in 80% o'clock of initial capacity, and what record the results are shown in the table 1.
Table 1
| The battery numbering | Density (the gram per centimeter of anodal coating 3) | Density (the gram per centimeter of negative pole coating 3) | 0.2C discharge capacity (MAH) | 2C discharge capacity (MAH) | Cycle-index (inferior) |
| ??C1 | ??2.8 | ??1.65 | ??920 | ??900 | ??700 |
| ??CC1 | ??2.2 | ??1.65 | ??720 | ??700 | ??630 |
| ??C2 | ??2.8 | ??1.65 | ??920 | ??900 | ??700 |
| ??CC2 | ??2.2 | ??1.65 | ??720 | ??700 | ??600 |
| ??C3 | ??2.8 | ??1.7 | ??960 | ??930 | ??730 |
| ??B1 | ??3.8 | ??1.3 | ??1400 | ??1300 | ??200 |
| ??BB1 | ??3.8 | ??1.1 | ??1350 | ??1250 | ??30 |
| ??B2 | ??3.8 | ??1.3 | ??1380 | ??1280 | ??180 |
| ??BB2 | ??3.8 | ??1.1 | ??1320 | ??1220 | ??30 |
As can be seen from Table 1: when adopting the battery of adhesive composition preparation of the present invention, can significantly improve the density of the coating of negative or positive electrode, improve the capacity and the cycle performance of battery, for example, the anodal coating of embodiment 1 density be 2.8 grams per cubic centimters, 0.2C discharge capacity is 920 MAHs, cycle-index is 700 times; The anodal coating of the preparation of Comparative Examples 1 density be 2.28 grams per cubic centimters, the 0.2C discharge capacity is 700 MAHs, cycle-index is 630 times.When using silica flour or alloy silicon as negative electrode active material, can greatly improve the battery B1 circulation 200 times of cycle performance such as embodiment 4 preparations after capacitance drop to 80% of initial capacity; And the battery BB1 of Comparative Examples preparation 30 capacitances that only circulate just drop to 80% of initial capacity.
Claims (12)
1, a kind of adhesive composition is characterized in that, said composition contains first binding agent and second binding agent, and wherein, the curing temperature of described first binding agent is greater than 150 ℃ to 500 ℃, and the curing temperature of described second binding agent is 50-150 ℃.
2, composition according to claim 1, wherein, the weight ratio of described first binding agent and described second binding agent is 1: 9 to 9: 1.
3, composition according to claim 1 and 2, wherein, described first binding agent is one or more in polyimides, epoxy resin, siloxane polymer, the phenolic resins; Described second binding agent is one or more in sodium carboxymethylcellulose, butadiene-styrene rubber, polytetrafluoroethylene, polyvinyl alcohol, polyurethane, polyvinylidene fluoride, vinylidene fluoride-TFE copolymer, vinylidene difluoride-hexafluoropropylene copolymer, hexafluoropropylene-TFE copolymer, the vinylidene fluoride-tetrafluoraoethylene-hexafluoropropylene copolymer.
4, a kind of positive electrode composition, said composition comprises positive active material, conductive agent and binding agent, it is characterized in that, described binding agent is any described adhesive composition of claim 1-3.
5, positive electrode composition according to claim 4, wherein, total weight with described positive active material, conductive agent and binding agent is a benchmark, the content of described binding agent is 0.3-15 weight %, the content of described positive active material is 83-98 weight %, and the content of described conductive agent is 1-10 weight %.
6, positive electrode composition according to claim 5, wherein, described positive active material is LiFePO4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F and LiFeO
2In one or more; Conductive agent is one or more in graphite, carbon fiber, carbon black, metal dust and the carbon fiber.
7, a kind of positive pole of lithium rechargeable battery, this positive pole comprise collector and the positive electrode that loads on the collector, it is characterized in that described positive electrode is any described positive electrode composition among the claim 4-6.
8, a kind of negative material composition, said composition comprises negative electrode active material and binding agent, it is characterized in that, described binding agent is any described adhesive composition of claim 1-3.
9, negative material composition according to claim 8 wherein, is a benchmark with the total weight of described negative electrode active material and binding agent, and the content of described binding agent is 0.3-20 weight %, and the content of described negative electrode active material is 80-99.7 weight %.
10, negative material composition according to claim 8, wherein, described negative electrode active material is one or more in silicon materials, tin and the carbonaceous material.
11, a kind of negative pole of lithium rechargeable battery, this negative pole comprise collector and the negative material that loads on the collector, it is characterized in that described negative material is any described negative material composition among the claim 8-10.
12, a kind of lithium rechargeable battery, this lithium rechargeable battery comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in the battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that described positive pole of described just very claim 7 and/or described negative pole are the described negative pole of claim 11.
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|---|---|---|---|
| CN200810210167A CN101662026A (en) | 2008-08-29 | 2008-08-29 | Bonder composition, compositions of anode and cathode materials, anode, cathode and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810210167A CN101662026A (en) | 2008-08-29 | 2008-08-29 | Bonder composition, compositions of anode and cathode materials, anode, cathode and battery |
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| CN101662026A true CN101662026A (en) | 2010-03-03 |
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| CN102130331A (en) * | 2011-01-26 | 2011-07-20 | 郭兆靖 | Method for modifying lithium battery |
| CN102610789A (en) * | 2011-01-20 | 2012-07-25 | 三星Sdi株式会社 | Electrode for lithium secondary battery and lithium secondary battery including the same |
| CN103268955A (en) * | 2013-01-23 | 2013-08-28 | 浙江地坤键新能源科技有限公司 | Composite gel polymer electrolyte and preparation method and application thereof |
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| CN107641484A (en) * | 2016-07-22 | 2018-01-30 | 三星电子株式会社 | Adhesive, the method for preparing the adhesive and electrode and lithium battery including the adhesive |
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| CN102130331A (en) * | 2011-01-26 | 2011-07-20 | 郭兆靖 | Method for modifying lithium battery |
| CN103268955A (en) * | 2013-01-23 | 2013-08-28 | 浙江地坤键新能源科技有限公司 | Composite gel polymer electrolyte and preparation method and application thereof |
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| CN107641484A (en) * | 2016-07-22 | 2018-01-30 | 三星电子株式会社 | Adhesive, the method for preparing the adhesive and electrode and lithium battery including the adhesive |
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| CN108084897A (en) * | 2017-12-26 | 2018-05-29 | 成都新柯力化工科技有限公司 | A kind of power lithium-ion battery adhesive special |
| CN114361384A (en) * | 2021-12-31 | 2022-04-15 | 远景动力技术(江苏)有限公司 | Negative electrode, electrochemical device, and electronic apparatus |
| CN114361384B (en) * | 2021-12-31 | 2024-03-26 | 远景动力技术(江苏)有限公司 | Negative electrode, electrochemical device, and electronic apparatus |
| CN114583171A (en) * | 2022-01-20 | 2022-06-03 | 贵阳学院 | Lithium battery electrode adhesive and preparation method thereof |
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