CN102237526A - Lithium ion battery cathode slurry, cathode and battery - Google Patents
Lithium ion battery cathode slurry, cathode and battery Download PDFInfo
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- CN102237526A CN102237526A CN2010101665589A CN201010166558A CN102237526A CN 102237526 A CN102237526 A CN 102237526A CN 2010101665589 A CN2010101665589 A CN 2010101665589A CN 201010166558 A CN201010166558 A CN 201010166558A CN 102237526 A CN102237526 A CN 102237526A
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Abstract
The invention provides lithium ion battery cathode slurry, a cathode and a battery. The cathode slurry comprises a cathode active material, an agglomerant and a dispersing agent. The dispersing agent comprises a tartrate. With adopting the tartrate as the dispersing agent for the cathode slurry, dispersity of the cathode slurry is raised; viscosity and stability of the cathode slurry are improved; compatibility of the cathode slurry and electrolyte is improved, such that a SEI film with stable performance can be formed on the surface of the cathode, and decomposition of PC-based electrolyte can be avoided so as to improve battery performance.
Description
Technical field
The lithium ion battery negative and the battery that the present invention relates to a kind of lithium ion battery cathode slurry and prepare with this cathode size.
Background technology
Compare with other chemical power source, lithium rechargeable battery has the performance of many excellences, as the energy density height, have extended cycle life, advantage such as open circuit voltage height, memory-less effect, safety non-pollution.Through the develop rapidly of recent two decades, lithium rechargeable battery has been widely used in fields such as mobile phone, notebook computer, digital camera.Along with the rise of global oil price and the enhancing of people's environmental consciousness, no matter be research institution or enterprise, all sight is concerned about in the exploitation of electric automobile.The researcher generally believes that lithium rechargeable battery is a kind of the most potential chemical power source that is applied on the electric automobile.Compare with other mobile device, electric automobile proposes higher requirement to the performances such as cycle life, energy density, consistency of battery pack and large current discharging capability of battery.
Negative pole is as the active component of lithium ion battery, be the focus and the difficult point of research always, and because the grain diameter of negative electrode active materials such as adhesive particle particle diameter and graphite differs bigger, when preparing electrode paste, easily be coated on the large particle surface of negative electrode active material, and then cause slurry to disperse inequality, rheological characteristic and less stable.
Have now and disclose the branch calculation homogeneity that improves cathode size by the interpolation dispersant, but dispersion effect is still undesirable, still has stronger reunion, makes troubles to coating process, the performance of Zhi Bei battery is also undesirable simultaneously.
Simultaneously, propene carbonate class with good low temperature performance (PC yl) electrolyte of existing broad research (fusing point is for-49 degrees centigrade) battery, because the decomposition electric potential of propene carbonate class electrolyte is 2.7V, very easily decompose existing the use under the current potential 3V-4.2V on the negative active core-shell material surface, produce alkyl lithium carbonate and propylene gas, the gas that produces can impact by the anticathode particle, easily cause breaking of negative terminal surface particle, come off and the inactivation of partial electrode active material, reduce the discharge capacity first and the cycle performance of battery, simultaneously the compatibility of PC base electrolyte and graphite is relatively poor, brings obstacle to the practical application of this kind battery.
Summary of the invention
The present invention disperses inhomogeneous, rheological characteristic and less stable for the cathode size that overcomes prior art, be used in simultaneously and be subjected to the influence of electrolyte bigger in the battery, there is the problem that more seriously comes off, provide that a kind of rheological property is better, stability pole piece pliability stronger, that dressing strength reaches preparation well is higher and be subjected to the less lithium ion battery cathode slurry of influence of electrolyte, comprise negative active core-shell material, binding agent, solvent and dispersant, described dispersant comprises tartrate.
The present inventor finds, adopt tartrate can not only obviously improve the dispersiveness of cathode size as the dispersant of cathode size, and tartrate is originally as polymer form, can further form cross-linked network structure with binding agent, and then the adhesive property between increase binding agent and the particle, improve cathode size viscosity, the tartrate polymer is also by the interaction between Van der Waals force and the hydrogen bond simultaneously, make between binding agent and the graphite and form bridging, and then binding agent is uniformly distributed between the graphite granule, reduce the reunion of graphite granule, improve cathode size stability.
The present inventor is unexpected simultaneously finds, when cathode size of the present invention is used in the lithium ion battery, when particularly containing PC base electrolyte, can effectively stop PC base decomposition of electrolyte and coming off of graphite.Reason may be for having
The tartrate of structure has chiral structure, can react with the lithium salts in the electrolyte, generates lithium compound, forms effective SEI film in negative terminal surface, improves the reversible capacity of battery.Its decomposition electric potential is 2.3V simultaneously, be lower than the decomposition electric potential of propene carbonate class electrolyte, also can stop the decomposition of propene carbonate class electrolyte, the product that the back of sodium tartrate and propene carbonate class electrolyte reaction simultaneously forms comprises lithia, lithium fluoride etc., can further form the firm SEI film of one deck, prevent coming off of negative active core-shell material, improve the compatibility of PC base electrolyte and graphite in negative terminal surface.
The present invention provides a kind of discharge capacity first and the better lithium ion battery negative of cycle performance simultaneously, and it is coated on the negative electrode collector by above-mentioned cathode size, and drying, calendering prepare.
Another object of the present invention is to improve a kind of lithium ion battery, comprises battery container and is sealed in this battery container interior electrode group and electrolyte; The electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, negative pole is above-mentioned lithium ion battery negative.
Description of drawings
Fig. 1 a is the amplitude sweep figure of the battery cathode slurry of the embodiment of the invention 1, embodiment 6 and Comparative Examples 1 preparation, and wherein, " ■ " line is represented G ' storage modulu of embodiment 1,
Line is represented the G " loss modulus of embodiment 1; " zero " line is represented G ' storage modulu of embodiment 6, and " * " represents the G " loss modulus of embodiment 6; " " line is represented the G ' storage modulu of Comparative Examples 1, and " △ " line is represented the G " loss modulus of Comparative Examples 1;
Fig. 1 b is the rheological behavior figure of the battery cathode slurry of the embodiment of the invention 1, embodiment 6 and Comparative Examples 1 preparation;
Fig. 2 a is the amplitude sweep figure after the battery cathode slurry of the embodiment of the invention 1, embodiment 6 and Comparative Examples 1 preparation leaves standstill 24h, and wherein, " ■ " line is represented G ' storage modulu of embodiment 1,
Line is represented the G " loss modulus of embodiment 1; " zero " line is represented G ' storage modulu of embodiment 6, and " * " represents the G " loss modulus of embodiment 6; " " line is represented the G ' storage modulu of Comparative Examples 1, and " △ " line is represented the G " loss modulus of Comparative Examples 1;
Fig. 2 b is the amplitude sweep figure after the battery cathode slurry of the embodiment of the invention 1, embodiment 6 and Comparative Examples 1 preparation leaves standstill 24h;
Fig. 3 a, Fig. 3 b, Fig. 3 c are the stability resolution charts of the battery cathode slurry of the embodiment of the invention 1, embodiment 6 and Comparative Examples 1 preparation;
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The invention provides a kind of lithium ion battery cathode slurry, comprise negative active core-shell material, binding agent, reach dispersant, described dispersant comprises tartrate, and rheological property is better, stability pole piece pliability stronger, that dressing strength reaches preparation well is higher and be subjected to the influence of electrolyte less.
The preferred tartrate of the present invention is selected from one or more in sodium tartrate, potassium tartrate, sodium potassium tartrate tetrahydrate, potassium antimony tartrate or the sodium hydrogen tartrate.Reduce of the influence of other metal ions, prevent the stability that complex compound etc. forms influence electrode slurry and electrolyte electrolyte, and the self-discharge rate of reduction battery.
The present invention is a benchmark with the total amount of negative active core-shell material preferably, and hundred parts of content of the weight of dispersant are 0.001-3%, more preferably 0.03-2%.Reduce the consumption of dispersant, improved the specific capacity of battery.
Also comprise citrate in the preferred dispersants of the present invention; Further the binding agent of preferred this moment is the water system binding agent.The citrate polymer not only also can and binding agent form cross-linked network structure and increase adhesive property between binding agent and the particle, improve slurry viscosity, also can be by the interaction between Van der Waals force and the hydrogen bond, make between binding agent and the graphite and form bridging, and then binding agent is uniformly distributed between the graphite granule, reduce the reunion of graphite granule, improve slurry stability.Special its be tricarboxylic acid, pH value that can hydrolysis control cathode size is avoided the water system binding agent for the alkali condition sensitivity, is the viscosity change under the condition of 5.5-8 in the pH value, raising cathode size stability.The binding energy of tartrate and citrate is further optimized the rheological characteristic and the stability of cathode size simultaneously, reduces the consumption of dispersant simultaneously.Improve the specific capacity of battery.
The preferred water system binding agent of the present invention is selected from one or more in sodium carboxymethylcellulose, carboxyethyl cellulose, ethyl cellulose, carboxymethylethylcellulose, CMC, hydroxypropyl cellulose or the butadiene-styrene rubber; Citrate is selected from natrium citricum, one or more in potassium citrate or the lemon acid amide.
The weight ratio of preferred tartrate of the present invention and citrate is 0.01-3; The weight ratio of described citrate and water system binding agent is 0.002-0.67.
Preferably also contain solvent in the cathode size of the present invention, solvent can be water or water-soluble solvent, it also can be organic solvent, be that dispersant of the present invention can be used for the water system slurry, also can be used for oil is slurry, and solvent types can be adjusted according to the kind of negative active core-shell material and binding agent.Preferred solvent of the present invention is selected from one or more in water, n-formyl sarcolysine base pyrrolidones, ethanol or the benzene.Preferred solvent is water or water-soluble solvent, makes dispersant bring into play its special performance under the environment of water system binding agent and water, makes performance the best of dispersant and water system binding agent combination.The water system slurry has non-environmental-pollution, low cost and other advantages simultaneously, helps a large amount of technology production.
The preferred negative active core-shell material of the present invention is a native graphite, one or more in Delanium or the hard charcoal.Wherein, the grain diameter of negative active core-shell material is 5 microns-50 microns, and the grain diameter of binding agent is 50 nanometers-500 nanometers.The grain diameter of binding agent and negative active core-shell material differs bigger, the polymer tartrate is by the interaction between Van der Waals force and the hydrogen bond, make between binding agent and the negative active core-shell material and form bridging, and then binding agent is uniformly distributed between the negative electrode active particle, reduce the reunion of negative electrode active particle, improve cathode size stability.
Wherein, ratio the present invention of negative active core-shell material, binding agent and solvent is not particularly limited, can adjust flexibly material concentration according to the viscosity of the slurry coating of the composition of battery electrode active material, binding agent and the cathode size that will prepare and the requirement of operability, mode is conventionally known to one of skill in the art.In general the total amount with negative active core-shell material is a benchmark, and the consumption of binding agent is 3-6%, and the consumption of solvent is 80-120%.
The present invention provides a kind of lithium ion battery negative simultaneously, is coated on the negative electrode collector by above-mentioned cathode size, and drying, calendering prepare.
Wherein, negative electrode collector is for well known to a person skilled in the art various negative electrode collectors, for example, can be selected from aluminium foil, Copper Foil, nickel plated steel strip, the Punching steel strip one or more.
Wherein, drying, the step of calendering, the same with prior art, promptly drying usually under vacuum condition at 50-160 ℃, carry out under preferred 80-150 ℃.Calendering can be adopted this area rolling condition commonly used, such as the 0.5-3.0 MPa.
The preparation of negative pole can also comprise other steps, and for example, the cut-parts of reprocessing, cut-parts are as well known to those skilled in the art, after calendering is finished, cuts according to the anodal size of prepared battery request, obtains cathode pole piece.
The present invention provides lithium rechargeable battery simultaneously, comprises battery container and is sealed in this battery container interior electrode group and electrolyte; The electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, negative pole is above-mentioned negative pole.Because the present invention only relates to the improvement to the prior art lithium ion secondary battery negative pole, therefore other The Nomenclature Composition and Structure of Complexes to lithium rechargeable battery has no particular limits.
Electrolyte comprises electrolyte lithium salt and nonaqueous solvents.Wherein, electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Nonaqueous solvents is selected from one or more in ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl carbonate ester or the dimethoxy-ethane.Wherein, in the electrolyte, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
Barrier film has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery case with positive pole, negative pole and electrolyte.Described barrier film can be the general various barrier films in this area, such as by those skilled in the art in the modified poly ethylene felt of respectively producing the trade mark, modified polypropene felt, ultra-fine fibre glass felt, vinylon felt or the nylon felt of known each manufacturer production and wettability microporous polyolefin film through welding or the bonding composite membrane that forms.
Wherein, the technology that well known to a person skilled in the art is adopted in anodal preparation, and for example positive pole comprises anode sizing agent is coated on the positive electrode collector, and drying, calendering prepare.Anode sizing agent generally comprises positive active material, conductive agent, anodal binding agent and anodal solvent.
Positive active material can be any positive active material that can be purchased in the prior art, for example, can adopt all positive active materials that can be purchased, as LiFePO
4, Li
3V
2(PO
4)
3, LiMn
2O
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4F, LiFeO
2Perhaps ternary system Li
1+aL
1-b-cM
bN
cO
2, a, b, c represent molal quantity separately, wherein-0.1≤a≤0.2,0≤b≤1,0≤c≤1,0≤b+c≤1.0, L, M, N be among Co, Mn, Ni, Al, Mg, Ga, Sc, Ti, V, Cr, Fe, Cu and the Zn one or more.
Anodal binding agent can be the lithium ion cell positive binding agent of routine, is preferably in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and the butadiene-styrene rubber (SBR) one or more.
Positive electrode collector is a positive electrode collector known in those skilled in the art, for example can be selected from aluminium foil, Copper Foil or various Punching steel strip.
Anodal preparation method can adopt this area the whole bag of tricks commonly used, for example positive active material, anodal binding agent and conductive agent are prepared into the positive electrode slurries with anodal solvent, the viscosity that the addition of anodal solvent can be coated with according to the slurry of the anodal slurries that will prepare and the requirement of operability are adjusted flexibly, the anodal slurries that will obtain then are coated on the plus plate current-collecting body, dry compressing tablet, cut-parts obtain positive pole again.When with solvent the positive active material of above-mentioned positive electrode composition, anodal binding agent and conductive agent being prepared into the positive electrode slurries, reinforced order is not asked especially.Dry temperature can be 80-150 ℃, and can be 2-10 hour drying time.The method and the condition of calendering are method known in those skilled in the art.Anodal solvent can be a various anodal solvent 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 anodal solvent can be coated on the conducting base anode sizing agent and gets final product.
The preparation method of lithium rechargeable battery provided by the invention can be 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, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is a conventional amount used.
Unless stated otherwise, all kinds of solvents of the present invention and reagent are commercially available analytical reagent.
Below in conjunction with specific embodiment the present invention is further described.
(1) preparation of negative pole:
Elder generation is with the sodium tartrate of 2g, the 2g natrium citricum is dissolved in the 98.5ml water, in above-mentioned sodium tartrate and natrium citricum mixed liquor, add 1.5g sodium carboxymethylcellulose (CMC) (about 1 micron of average grain particle diameter), in above-mentioned mixed liquor, add 100g graphite (17 microns of average grain particle diameters) subsequently, stirred 2 hours, add 3g styrene-butadiene latex (SBR) (about average grain particle diameter 300 nanometers) again, use common four leaf oars to stir 0.5 hour, and then to obtain the pH value be 7 cathode size (graphite: CMC: sodium tartrate: natrium citricum: SBR: deionized water=100: 1.5: 2: 2: 3: 98.5).
This cathode size is coated on the Copper Foil equably, and at the pressure lower sheeting of 2 MPas, 300 ℃ of heat treatment is 24 hours under condition of nitrogen gas, and calendering then cuts into the negative plate of 416mm * 45mm, contains 3.2 gram negative active core-shell materials in each negative plate.
(2) Zheng Ji preparation
30 gram polytetrafluoroethylene are dissolved in about 500 grams make binder solution in the water, 940 gram Li-Ni-Mn-Co-Os (Ningbo JinHe New Materials Co., Ltd) join in the above-mentioned solution with graphite and the carbon fiber that 30 grams serve as conductive agent then, fully mix and make anode sizing agent, the mass ratio of graphite and carbon fiber is 100: 5, with tensile pulp machine this anode sizing agent is coated to thick 18 microns aluminium foil two sides equably.Through 125 ℃ of vacuum and heating dryings 1 hour, calendaring molding under 2.0 MPa pressure, cut-parts make the positive pole of millimeter (wide) * 130,360 millimeters (length) * 43.5 micron (thick), contain the positive active materials of 5.42 grams on every positive pole.
(3) preparation of battery
The polypropylene diaphragm and the cathode pole piece of above-mentioned anode pole piece, 20 micron thickness are overlapped into electric core successively, in the battery case of packing into, electrolyte are injected battery case with the amount of 3.8g/Ah, conventional LP053450 battery is made in sealing.Electrolyte contains LiPF
6And nonaqueous solvents, LiPF in the electrolyte
6Concentration be 1 mol, nonaqueous solvents is the mixed solvent of propene carbonate and dimethyl carbonate.
Adopt method and step preparation positive pole, negative pole and the battery identical with embodiment 1, different is sodium tartrate, the 1g natrium citricum that adds 0.2g in the cathode size, and preparation pH value is 6.5 cathode size (graphite: CMC: sodium tartrate: natrium citricum: SBR: deionized water=100: 1.5: 0.2: 1: 3: 98.5).
Adopt method and step preparation positive pole, negative pole and the battery identical with embodiment 1, different is sodium tartrate, the 3g natrium citricum that adds 8.5g in the cathode size, and preparation pH value is 7.5 cathode size (graphite: CMC: sodium tartrate: natrium citricum: SBR: deionized water=100: 1.5: 8.5: 3: 3: 98.5).
Embodiment 4
Adopt method and step preparation positive pole, negative pole and the battery identical with embodiment 1, different is sodium tartrate, the 0.5g natrium citricum that adds 2g in the cathode size, and preparation pH value is 7 cathode size (graphite: CMC: sodium tartrate: natrium citricum: SBR: deionized water=100: 1.5: 2: 0.5: 3: 98.5).
Embodiment 5
Adopt method and the step preparation positive pole identical with embodiment 1, negative pole and battery, different is cathode size be prepared as sodium tartrate with 2g, the 2g natrium citricum is dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP) of 75ml, 1.5g Kynoar (PVDF) (about 2 microns of average grain particle diameters), be dissolved in the 23.5mlN-N-methyl-2-2-pyrrolidone N-, two kinds of solution are mixed, the back adds 100g graphite (about 17 microns of average grain particle diameters), use common four leaf oars to stir 2 hours, and then the cathode size that obtains (graphite: PVDF: sodium tartrate: natrium citricum: NMP=100: 1.5: 2: 2: 98.5).
Embodiment 6
Adopt method and step preparation positive pole, negative pole and the battery identical with embodiment 1, the dispersant that different is adds in the cathode size has only the sodium tartrate of 4g.
Embodiment 7
Adopt method and step preparation positive pole, negative pole and the battery identical with embodiment 1, different is that battery electrolyte contains LiPF
6And nonaqueous solvents, LiPF described in the electrolyte
6Concentration be 1 mol, nonaqueous solvents is an ethylene carbonate (EC) and diethyl carbonate (DMC) weight ratio is 1: 1 the ethylene carbonate and the mixed solvent of diethyl carbonate.
Comparative Examples 1
Adopt the method identical with embodiment 1 and the step preparation is anodal, negative pole and battery, different is not add sodium tartrate and natrium citricum in the cathode size, and the polyethylene glycol of adding 4g.
Performance test:
1. cathode size rheology testing
Adopt the rotation rheology tester of Physica MCR 301 models of Anton Paar company, carry out rheology testing according to American Society Testing and Materials mark ASTM D 7175-2005 to having placed embodiment 1, embodiment 6 after 1 hour and the cathode size of Comparative Examples 1, (scan amplitude figure is at 25 ℃, normal pressure, angular speed 10s for test result such as Fig. 1 a
-1Under the constant condition, in the test shear strain clump 0.1%-1000% change procedure, the situation of change of storage modulu and loss modulus) and Fig. 1 b (flow diagram is at 25 ℃, under the condition of normal pressure, tests shear rate from 0.01s
-1-1000s
-1In the change procedure, the viscosity change situation);
Adopt the rotation rheology tester of Physica MCR 301 models of Anton Paar company, carry out rheology testing, test result such as Fig. 2 a (scan amplitude figure) and Fig. 2 b (flow diagram) according to American Society Testing and Materials mark ASTM D 7175-2005 to having placed embodiment 1, embodiment 6 after 24 hours and the cathode size of Comparative Examples 1;
2. cathode size stability test
Use Formulaction stability separating apparatus respectively the cathode size of embodiment 1, embodiment 6 and Comparative Examples 1 preparation to be carried out stability sign, test result such as Fig. 3.
3. pole piece dressing performance test
Use MODEL 1220S type contact engaging and separating force experimental machine to embodiment 1, the negative pole (the pole piece specification is 4cm*10cm) of embodiment 6 and Comparative Examples 1 preparation carries out dressing strength test, test result such as Fig. 3.
4, reversible specific capacity test: the battery of embodiment 1-7 and Comparative Examples 1 preparation is placed on the new Weir-3000 type electrochemical property test instrument, with 0.075A electric current charge-discharge test, result such as table 1.
5, battery multiplying power discharging property test
The battery of embodiment 1-7 and Comparative Examples 1 preparation is placed on the new Weir-3000 type electrochemical property test instrument, with the 0.075A current charges, with 0.075A, 0.75A, 2.25A current discharge, voltage range 3V-4.2V, record discharge capacity, test result such as table 2.
6, discharge capacity test first:
Electrode slice with embodiment 1-7 and Comparative Examples 1 preparation is a positive pole, with the lithium metal is negative pole, produce model and be 2016 button cell, above-mentioned battery is placed on the new Weir-3000 type electrochemical property test instrument, voltage range 3V-4.2V, discharge and recharge with the 0.075A electric current, write down its discharge capacity first.Test result such as table 3.
7, cycle performance test
The battery of embodiment 1-7 and Comparative Examples 1 preparation is placed on the new Weir-3000 type electrochemical property test instrument, and voltage range 3V-4.2V discharges and recharges with the 0.075A electric current, writes down its charge/discharge capacity, test result such as table 4.
Table 1
| Battery | Initial charge specific capacity (mAh/g) | First discharge specific capacity (mAh/g) | Capability retention (%) |
| |
760 | 750 | 98.7 |
| |
724 | 704 | 97.3 |
| |
717 | 691 | 96.4 |
| Embodiment 4 | 703 | 681 | 94.9 |
| Embodiment 5 | 697 | 671 | 96.3 |
| Embodiment 6 | 742 | 722 | 97.3 |
| Embodiment 7 | 757 | 736 | 97.2 |
| Comparative Examples 1 | 680 | 644 | 94.7 |
Table 2
| Battery | 0.075A the time capacity (mAh/g) | 0.75A the time capacity (mAh/g) | 2.25A the time capacity (mAh/g) |
| |
760 | 730 | 680 |
| |
724 | 694 | 644 |
| |
717 | 681 | 631 |
| Embodiment 4 | 703 | 667 | 617 |
| Embodiment 5 | 697 | 661 | 611 |
| Embodiment 6 | 742 | 712 | 662 |
| Embodiment 7 | 757 | 726 | 678 |
| Comparative Examples 1 | 680 | 644 | 594 |
Table 3
| Battery | Capacity (mAh/g) |
| |
348 |
| |
330 |
| |
320 |
| Embodiment 4 | 314 |
| Embodiment 5 | 309 |
| Embodiment 6 | 332 |
| Embodiment 7 | 326 |
| Comparative Examples 1 | 302 |
Table 4
| Battery | Capacity (mAh/g) first | 150 circulation back capacity (mAh/g) |
| |
767 | 743 |
| |
754 | 700 |
| |
727 | 687 |
| Embodiment 4 | 733 | 651 |
| Embodiment 5 | 706 | 661 |
| Embodiment 6 | 740 | 691 |
| Embodiment 7 | 757 | 733 |
| Comparative Examples 1 | 694 | 555 |
Strong and the good stability of electrode slurry good dispersion of the present invention, dressing performance is easy to store and slurry, the electrode high conformity of preparation, and pole piece thickness is evener one, has improved rate of finished products, has reduced production cost.The PC base electrolyte battery performance that particularly is applied to excellent performance is more excellent.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. a lithium ion battery cathode slurry is characterized in that, comprises negative active core-shell material, binding agent, solvent and dispersant, and described dispersant comprises tartrate.
2. cathode size according to claim 1 is characterized in that described tartrate is selected from one or more in sodium tartrate, potassium tartrate, sodium potassium tartrate tetrahydrate, potassium antimony tartrate or the sodium hydrogen tartrate.
3. cathode size according to claim 1 is characterized in that, is benchmark with the total amount of negative active core-shell material, and hundred parts of content of the weight of described dispersant are 0.001-3%.
4. cathode size according to claim 1 is characterized in that described dispersant also comprises citrate; Described binding agent is the water system binding agent.
5. cathode size according to claim 4 is characterized in that, the pH value of described cathode size is 5.5-8.
6. cathode size according to claim 4, it is characterized in that described water system binding agent is selected from one or more in sodium carboxymethylcellulose, carboxyethyl cellulose, ethyl cellulose, carboxymethylethylcellulose, CMC, hydroxypropyl cellulose or the butadiene-styrene rubber;
Described citrate is selected from natrium citricum, one or more in potassium citrate or the lemon acid amide.
7. cathode size according to claim 4 is characterized in that, the weight ratio of described tartrate and citrate is 0.01-3; The weight ratio of described citrate and water system binding agent is 0.002-0.67.
8. cathode size according to claim 1 is characterized in that, described solvent is selected from one or more in water, ethanol, benzene or the n-formyl sarcolysine base pyrrolidones.
9. cathode size according to claim 1, it is characterized in that described negative active core-shell material is a native graphite, one or more in Delanium or the hard charcoal, the grain diameter of described negative active core-shell material is 5 microns-50 microns, and the grain diameter of described binding agent is 50 nanometers-500 nanometers.
10. a lithium ion battery negative is characterized in that, described negative pole is coated on the negative electrode collector by any described cathode size of claim 1-9, and drying, calendering prepare.
11. a lithium ion battery is characterized in that, comprises battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and wherein, described negative pole is the described lithium ion battery negative of claim 10.
12. lithium ion battery according to claim 11 is characterized in that, described electrolyte comprises electrolyte lithium salt and nonaqueous solvents; Described electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more; Described organic solvent is selected from one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl carbonate ester or the dimethoxy-ethane.
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| CN2010101665589A CN102237526A (en) | 2010-04-29 | 2010-04-29 | Lithium ion battery cathode slurry, cathode and battery |
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| CN2010101665589A CN102237526A (en) | 2010-04-29 | 2010-04-29 | Lithium ion battery cathode slurry, cathode and battery |
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| CN2010101665589A Pending CN102237526A (en) | 2010-04-29 | 2010-04-29 | Lithium ion battery cathode slurry, cathode and battery |
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| CN103000866A (en) * | 2012-12-03 | 2013-03-27 | 彩虹集团公司 | Negative pole material of lithium ion battery and manufacturing method of negative pole of battery |
| CN103840130A (en) * | 2014-03-24 | 2014-06-04 | 四川剑兴锂电池有限公司 | Lithium battery carbon cathode capable of preventing over-discharging |
| CN104428926A (en) * | 2012-09-06 | 2015-03-18 | 株式会社吴羽 | Negative electrode for non-aqueous electrolyte secondary battery |
| CN104718657A (en) * | 2012-11-21 | 2015-06-17 | 株式会社Lg化学 | Lithium secondary battery |
| CN105229824A (en) * | 2013-05-23 | 2016-01-06 | 日本瑞翁株式会社 | Secondary battery negative pole paste compound, secondary battery cathode and secondary cell |
| CN105869709A (en) * | 2016-04-22 | 2016-08-17 | 苏州协鑫集成科技工业应用研究院有限公司 | Electrode slurry and preparation method therefor |
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| CN110048082A (en) * | 2019-04-03 | 2019-07-23 | 合肥国轩高科动力能源有限公司 | Method for reducing orientation value of graphite negative pole piece of lithium ion battery and pole piece obtained by method |
| WO2019205079A1 (en) * | 2018-04-27 | 2019-10-31 | Dow Global Technologies Llc | Ethyl cellulose as a dispersant for lithium ion battery cathode production |
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| CN104718657A (en) * | 2012-11-21 | 2015-06-17 | 株式会社Lg化学 | Lithium secondary battery |
| US9660266B2 (en) | 2012-11-21 | 2017-05-23 | Lg Chem, Ltd. | Lithium secondary battery |
| US9853288B2 (en) | 2012-11-21 | 2017-12-26 | Lg Chem, Ltd. | Lithium secondary battery |
| CN103000866A (en) * | 2012-12-03 | 2013-03-27 | 彩虹集团公司 | Negative pole material of lithium ion battery and manufacturing method of negative pole of battery |
| CN105229824A (en) * | 2013-05-23 | 2016-01-06 | 日本瑞翁株式会社 | Secondary battery negative pole paste compound, secondary battery cathode and secondary cell |
| CN105229824B (en) * | 2013-05-23 | 2017-07-18 | 日本瑞翁株式会社 | Secondary battery negative pole paste compound, secondary battery cathode and secondary cell |
| CN103840130A (en) * | 2014-03-24 | 2014-06-04 | 四川剑兴锂电池有限公司 | Lithium battery carbon cathode capable of preventing over-discharging |
| CN105869709A (en) * | 2016-04-22 | 2016-08-17 | 苏州协鑫集成科技工业应用研究院有限公司 | Electrode slurry and preparation method therefor |
| CN107919459A (en) * | 2017-11-29 | 2018-04-17 | 中航锂电（洛阳）有限公司 | Preparation method, anode plate for lithium ionic cell and the lithium ion battery of anode plate for lithium ionic cell |
| WO2019205079A1 (en) * | 2018-04-27 | 2019-10-31 | Dow Global Technologies Llc | Ethyl cellulose as a dispersant for lithium ion battery cathode production |
| US11581527B2 (en) | 2018-04-27 | 2023-02-14 | Dow Global Technologies Llc | Ethyl cellulose as a dispersant for lithium ion battery cathode production |
| CN109560287A (en) * | 2018-11-20 | 2019-04-02 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium battery collector and preparation method thereof |
| CN109560254A (en) * | 2018-11-20 | 2019-04-02 | 陕西煤业化工技术研究院有限责任公司 | A kind of lithium battery electrode plate and preparation method thereof |
| CN109560287B (en) * | 2018-11-20 | 2021-06-15 | 陕西煤业化工技术研究院有限责任公司 | Lithium battery current collector and preparation method thereof |
| CN110048082A (en) * | 2019-04-03 | 2019-07-23 | 合肥国轩高科动力能源有限公司 | Method for reducing orientation value of graphite negative pole piece of lithium ion battery and pole piece obtained by method |
| CN114749462A (en) * | 2022-04-06 | 2022-07-15 | 北京盈丰利泰科贸有限公司 | Recycling process of air conditioner residues |
| CN117239124A (en) * | 2022-06-06 | 2023-12-15 | 比亚迪股份有限公司 | Preparation method of electrode slurry, electrode slurry and negative electrode plate |
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Application publication date: 20111109 |