CN101207204A - Lithium ion battery anode material and lithium ion battery and anode containing the material - Google Patents
Lithium ion battery anode material and lithium ion battery and anode containing the material Download PDFInfo
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Abstract
The invention relates to lithium ion battery positive pole material, which includes lithium metal phosphate, bonding agent and electric conducting agent. The invention is characterized in that the positive pole active material also includes dispersing agent, and the dispersing agent is selected from one or more of polyacrylamide, polyacrylate, polyurethane, polyvinylpyrrolidone, polyisobutylene succimide, polyethylene oxide ether, hydroxy ethyl cellulose, dodecyl polyethylene oxide ester, fatty acid polyethylene oxide ester, alkoxy poly epoxy acrylate, poly caprolactone, polystyrene-ethylene pyrrolidone, polystyrene-N and N-divinyl acrylamide. The battery of the positive pole material provided by the invention, and the capacity, the internal resistance, charging and the heavy current discharging performance and the cycle performance of the battery are obviously improved.
Description
Technical field
The invention relates to a kind of anode material for lithium-ion batteries and the positive pole and the lithium ion battery that contain this material.
Background technology
Lithium ion battery has operating voltage height, in light weight, outstanding feature such as energy density is big, self discharge is little, have extended cycle life, memory-less effect, non-environmental-pollution, security performance are good, it is the higher a kind of portable ideal battery of present capacitance, can be applicable to video camera, move electronic installations such as electricity work, notebook computer and Portable Measurement Instrument, also is the first-selected power supply of light-duty high-energy power batteries such as following electric automobile, space flight, satellite, submarine, underwater robot.
Therefore lithium ion battery is widely used owing to having premium properties, and along with the developing rapidly of products such as modern mobile electronic device and communication apparatus, people are to being used for the demands for higher performance of these product power supplys.
Battery anode active material is one of key technology of lithium ion battery development.In the positive active material of commercial at present lithium rechargeable battery, LiCoO
2Rely on good circulation and bigger discharge capacity and high discharge platform and occupied the market share greater than 95%.But LiCoO
2The defective that can't remedy is arranged itself, the one, cobalt belongs to rare metal, and the reserves in the earth's crust are few, thereby cost an arm and a leg; The 2nd, LiCoO
2As the battery of negative material over-charging of battery or when overheated can with electrolyte generation vigorous reaction, emits a large amount of heats and cause battery to catch fire or explode, so security performance is relatively poor.
Since the eighties of last century the nineties, the low LiNiO that simultaneously environment is not had pollution of price
2, LiMn
2O
4Be considered to most possibly substitute LiCoO always
2Material.
Studies show that in recent years, LiNiO
2The layer structure poor stability, stoichiometric LiNiO
2Be difficult at low temperatures synthesize, and the mixing occupy-place of lithium nickel can take place under the high temperature synthesis condition.By the control of accurate condition (in the oxygen atmosphere under 750 ℃ of temperature roast 24 hours), just can synthesize LiNiO
2It is that higher initial specific capacity (initial charge capacity reaches 200 Milliampere Hour/grams) is arranged, but cycle performance is poor especially, and capacity promptly is lower than LiCoO after 10 circulations
2
LiMn
2O
4Though synthetic simple, low price and fail safe are good, LiMn
2O
4Specific capacity little (120 Milliampere Hour/gram), and the cycle life of (for example more than 55 ℃) is relatively poor under hot conditions, and although mix and chemical surface treatment through composition, cycle life still can't satisfy the requirement of actual use.Therefore, lithium battery industry, particularly high-power dynamic lithium battery needs that a kind of cost is lower, capacity more greatly and safer positive active material.
LiFePO
4Fail safe is good, good stability, asepsis environment-protecting, however LiFePO
4Material is because special olivine structural, poorly conductive, and specific capacity is low, the LiFePO of preparation at present
4Material is controlled in the littler particle size range usually, has improved single LiFePO in this way
4The electronic conductivity of particle and ionic conductivity, but contact point mutual when the positive active material that adopts small particle diameter can cause particle bond reduces, thereby greatly reduce the adhesion strength that reaches active material and collector between the active material, the minimizing of contact point has also reduced the intergranular conductivity of positive electrode between the active material, the scattering problem of electrode active material does not solve in addition, cause the slurry viscosity that makes excessive, therefore the battery of preparation have that capacitance is little, internal resistance big, the shortcoming of high rate during charging-discharging and cycle performance difference.
Summary of the invention
The objective of the invention is that existing capacity of lithium ion battery is little, internal resistance big in order to overcome, the shortcoming of high rate during charging-discharging and cycle performance difference, provide a kind of and can make that battery has that capacity is big, internal resistance is little, the positive electrode active materials of high rate during charging-discharging and good cycle and contain the positive pole and the lithium ion battery of this positive electrode active materials.
Anode active material of lithium ion battery provided by the invention contains lithium metal phosphates, binding agent and conductive agent, wherein, this positive electrode active materials also contains dispersant, described dispersant is selected from polyacrylamide, the polypropylene acid esters, polyurethane, polyvinylpyrrolidone, polyisobutene succinimide, poly(ethylene oxide) ether, hydroxyethylcellulose, dodecyl poly(ethylene oxide) ester, fatty acid polyglycol oxirane ester, alkoxyl polyalkylene oxide acrylate, polycaprolactone, polystyrene-vinyl pyrrolidone, polystyrene-N, one or more in the N-divinyl acrylamide.
Lithium ion cell positive provided by the invention comprises collector and/or is filled in positive electrode active materials on the collector that wherein, described positive electrode is an anode material for lithium-ion batteries provided by the invention.
Lithium ion battery provided by the invention comprises pole piece, nonaqueous electrolytic solution and battery container, described pole piece and nonaqueous electrolytic solution are sealed in the battery container, described pole piece comprises positive pole, negative pole and barrier film, wherein, and described lithium ion cell positive just very provided by the invention.
In the battery anode active material provided by the invention, owing to added dispersant the conductive agent of high surface is distributed in the positive pole equably, the conductive agent of high-specific surface area can effectively improve LiFePO
4The intergranular electronic conductivity of positive electrode active materials.The adding of HMW binding agent has further solved LiFePO
4After positive electrode active materials and high-specific surface area add, between the positive electrode active materials particle and the adhesion problem between positive electrode particle and the conductive agent, make battery have high power capacity, low internal resistance, more excellent high rate during charging-discharging and cycle performance.
Embodiment
Positive electrode active materials provided by the invention contains lithium metal phosphates, binding agent and conductive agent, wherein, this positive electrode active materials also contains dispersant, described dispersant is selected from polyacrylamide, polypropylene acid esters, polyurethane, polyvinylpyrrolidone, polyisobutene succinimide, poly(ethylene oxide) ether, hydroxyethylcellulose, dodecyl poly(ethylene oxide) ester, fatty acid polyglycol oxirane ester, alkoxyl polyalkylene oxide acrylate, polycaprolactone, polystyrene-vinyl pyrrolidone, polystyrene-N, one or more in the N-divinyl acrylamide.
The dispersant of HMW can make the conductive agent of high surface be distributed in the positive pole equably, and agglomeration does not take place, and therefore, preferred molecular weight of the present invention is the preferably polyethylene pyrrolidones (PVP) of 1000-200000.Described dispersant all can be commercially available.
Battery anode active material provided by the invention, lithium metal phosphates in this positive electrode active materials, binding agent, dispersant and conductive agent content can in very large range change, under the preferable case, amount with lithium metal phosphates is a benchmark, the content of conductive agent is 1%-15% weight %, the content of binding agent is 1%-20% weight %, the content of dispersant is 0.1%-5% weight %, more preferably, amount with lithium metal phosphates is a benchmark, the content of conductive agent is 2-10 weight %, and the content of binding agent is 2-15 weight %, and the content of dispersant is 0.2-2 weight %.
The kind of described conductive agent is conventionally known to one of skill in the art, and for example, described conductive agent can be selected from one or more in acetylene black, superconduction carbon black, electrically conductive graphite, conductive carbon fibre, the metal dust.
The conductive agent of high-specific surface area can effectively improve LiFePO
4The intergranular electronic conductivity of positive electrode, make battery have high power capacity, low internal resistance, has more excellent high rate during charging-discharging simultaneously, therefore the preferred specific area of the present invention is that the conductive agent of 100-2000 meters squared per gram, particularly surface area are the acetylene black and/or the superconduction carbon black of 100-2000 meters squared per gram.
Battery anode active material provided by the invention, the phosphate metal lithium salts that adopts olivine structural is as positive active material, and the molecular formula of this phosphate metal lithium salts is LiMPO
4, wherein M be among Fe, Mn, Co or the Ni one or more.The phosphate metal lithium salts of olivine structural can be commercially available, and also can adopt known method to prepare.
The phosphate metal lithium salts of olivine structural is because this body structure is more stable, the bond energy of P-O is very high, and therefore in the ordinary course of things, the P-O key is not easy fracture, can precipitated oxygen yet, so the battery that adopts olivine structural phosphate metal lithium salts to make has high security performance.
Battery anode active material provided by the invention, described binding agent can be usually as the various binding agents of anode binding agent, as being selected from Kynoar, polyvinyl alcohol, acid polyethylene butyral, polyacrylic acid formicester, carboxymethyl cellulose, methylcellulose, hydroxypropyl methylcellulose, the ethyl cellulose one or more.
The HMW binding agent can solve LiFePO
4After positive electrode and high-specific surface area add, between the positive electrode particle and the adhesion problem between positive electrode active materials particle and the conductive agent, make the cycle performance of battery obtain great lifting, therefore preferred molecular weight of the present invention is that the binding agent of 100000-2000000, particularly molecular weight are polyvinylidene fluoride and or the poly-inclined to one side tetrafluoroethene of 100000-2000000.
The preparation method of positive electrode active materials provided by the invention comprises lithium metal phosphates, binding agent and conductive agent mix, wherein, when mixing, also add dispersant, described dispersant is selected from polyacrylamide, the polypropylene acid esters, polyurethane, polyvinylpyrrolidone, polyisobutene succinimide, poly(ethylene oxide) ether, hydroxyethylcellulose, dodecyl poly(ethylene oxide) ester, fatty acid polyglycol oxirane ester, alkoxyl polyalkylene oxide acrylate, polycaprolactone, polystyrene-vinyl pyrrolidone, polystyrene-N, one or more in the N-divinyl acrylamide.
Lithium ion cell positive provided by the invention comprises collector and coating and/or is filled in positive electrode active materials on the collector that described positive electrode active materials is a positive electrode active materials provided by the invention.
Because the present invention only relates to the improvement to anode material for lithium-ion batteries, be not particularly limited forming anodal collector, can be plus plate current-collecting body conventional in the lithium ion battery, in specific embodiments of the present invention, use aluminium foil as plus plate current-collecting body.
Lithium ion cell positive provided by the invention can obtain by prepared in various methods, for example can apply by the slurry that will contain positive electrode active materials provided by the invention and solvent and/or be filled on the collector, dry, pressing mold or do not obtain behind the pressing mold, the described slurry that contains positive electrode active materials provided by the invention and solvent can by earlier with lithium metal phosphates and conductive agent dry powder blend evenly after, mix and obtain with adhesive, solvent or adhesive binder solution again with solvent formation; It is even with lithium metal phosphates and solvent also can to pass through elder generation, and then mixes with conductive agent, obtains slurry.Owing to contain water miscible enol based polyalcohol in the adhesive and conductive agent can not reunited in water, therefore, described solvent is preferably water.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described collector to get final product.Method and condition dry, pressing mold are conventionally known to one of skill in the art.
The negative pole, barrier film and the nonaqueous electrolytic solution that form lithium ion battery of the present invention can be conventional negative pole, barrier film, the nonaqueous electrolytic solution that uses in this area.
For example, described negative pole comprises collector and coating and/or is filled in negative material on the collector that described negative material comprises negative electrode active material and adhesive.
Described negative electrode active material is not particularly limited, can use embedding of this area routine to disengage the negative electrode active material of lithium, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, preferred electrographite.
Described negative material can also comprise conductive agent, and described conductive agent is not particularly limited, and can be the cathode conductive agent of this area routine, such as in ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive carbon black and the electrically conductive graphite one or more.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
The kind of described adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR); In general, according to the difference of adhesive therefor kind, be benchmark with the weight of negative electrode active material, the content of adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
Under the preferable case, described negative pole adhesive adopts the mixture of cellulose-based polymer and rubber latex, as the mixture of cellulose-based polymer and butadiene-styrene rubber (SBR).The consumption of described cellulose-based polymer and butadiene-styrene rubber is conventionally known to one of skill in the art.
Negative current collector can be for negative current collector conventional in the lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as negative current collector in specific embodiments of the present invention.
Described barrier film is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described pole piece and nonaqueous electrolytic solution are contained in the battery case together.Described barrier film can be selected from various barrier films used in the lithium ion battery, as the high molecular polymer microporous membrane, comprises polypropylene microporous membrane and polypropylene and poly MULTILAYER COMPOSITE microporous membrane.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9 gram/ampere-hour, and the concentration of electrolyte is generally the 0.5-2.9 mol.
The following examples will the invention will be further described.
Embodiment 1
This embodiment illustrates lithium ion anode material provided by the invention and contains the positive pole and the lithium ion battery of this positive electrode.
The preparation of positive electrode
With molecular weight 300000 polyvinylidene fluoride (Japanese Wu Yu chemical industry) binding agent, LiFePO
4, specific area is that the acetylene black of 1000 meters squared per gram and molecular weight are 5000 polyvinylpyrrolidone (universal love newly joins friendly chemical industry) dispersant, presses LiFePO
4: acetylene black: Kynoar: polyvinylpyrrolidone is 100: 4: 4: the mixed of 1 (weight) obtains positive electrode provided by the invention.
Anodal preparation
Total amount with positive electrode is as the criterion, the positive electrode that obtains is scattered in the N-methyl pyrrolidone of 60% weight ratio, fully be mixed and made into slurry, this slurry is uniformly coated on 20 microns the aluminium foil, after 120 ℃ of oven dry of temperature, after being calendered to 0.170 millimeter of thickness, cut the positive plate of 43 millimeters of 450 mm wides of growing up; Wherein positive plate contains 5.5 gram positive active material LiFePO
4
The preparation of negative pole
With molecular weight is that 300000 polyvinylidene fluoride (Japanese Wu Yu chemical industry) and Delanium are made negative material with the ratio of 5: 100 (weight), total amount with the negative pole material is a benchmark, negative material is scattered in the N-methyl pyrrolidone (the occasion chemical industry is praised in Shanghai) of 60% weight ratio, fully be mixed and made into slurry, evenly hang down this slurry on the Copper Foil that is coated on 20 microns, dry down 120 ℃ of temperature, cut the negative plate of 0.120 millimeter of growth 470 mm wides 45 millimeters thick after the calendering, negative plate contains 2.5 gram Delaniums.
The preparation of electrolyte
In the mixed solvent that with volume ratio is the ethylene carbonate that mixes at 1: 1: 1, diethyl carbonate, methyl ethyl carbonate, dissolve LiPF
6, make LiPF
6Concentration be 1.0 mol, be prepared into nonaqueous electrolytic solution.
The preparation of battery
Dividing plate with the microporosity polyethylene film that inserts 25 micron thickness between the above-mentioned positive and negative electrode constitutes is wound into helical form then, makes the electrode body of winding-structure.Electrode body is inserted in the square shell of aluminum, the body that will go between is welded on and covers, shell and lid are stitched postwelding, inject 3.5 gram electrolyte from inlet, sealing was then placed 24 hours down for 45 ℃, make electrode slice, negative plate and dividing plate impregnation electrolyte fully, changing into (with 70 milliamperes of electric current constant current charges 8 hours) makes and makes thick 5 millimeters, wide 34 millimeters, high 50 millimeters square lithium ion battery A1.
Comparative Examples 1
Method according to embodiment 1 prepares battery, and different is not add the polyethylene of dispersing agent pyrrolidones.Make thick 5 millimeters, wide 34 millimeters, high 50 millimeters reference square lithium ion battery CA1.
Embodiment 2
This embodiment illustrates lithium ion anode material provided by the invention and contains the positive pole and the lithium ion battery of this positive electrode.
Method according to embodiment 1 prepares battery, not being both conductive agent is the superconduction carbon black of surface area 2000 meters squared per gram, binding agent is that molecular weight is 2000000 poly-inclined to one side tetrafluoroethene (Japanese Wu Yu chemical industry), dispersant is molecular weight 2000 hydroxyethylcelluloses (Xiangtai Fiber Co., Ltd.), presses LiFePO
4: superconduction carbon black: polytetrafluoroethylene: polyacrylamide is 100: 15: 1: (weight) ratio of 0.1, make thick 5 millimeters, wide 34 millimeters, high 50 millimeters square lithium ion battery A2.
Embodiment 3
This embodiment illustrates lithium ion anode material provided by the invention and contains the positive pole and the lithium ion battery of this positive electrode.
Method according to embodiment 1 prepares battery, not being both conductive agent is the superconduction carbon black of surface area 500 meters squared per gram, binding agent is that molecular weight is 100000 polyvinylidene fluoride (Japanese Wu Yu chemical industry), dispersant is the polyvinylpyrrolidone (the occasion chemical industry is praised in Shanghai) of molecular weight 200000, presses LiFePO
4: superconduction carbon black and conductive carbon fibre: Kynoar: polyvinylpyrrolidone is 100: 1: 20: the ratio of 5 (weight), make thick 5 millimeters, wide 34 millimeters, high 50 millimeters square lithium ion battery A3.
Embodiment 4
This embodiment illustrates lithium ion anode material provided by the invention and contains the positive pole and the lithium ion battery of this positive electrode.
Method according to embodiment 1 prepares battery, is not both the acetylene black that conductive agent is surface area 400 meters squared per gram, and binding agent is that molecular weight is 500000 polytetrafluoroethylene (Japanese Wu Yu chemical industry), and dispersant is the polyacrylamide of molecular weight 10000, presses LiFePO
4: superconduction carbon black: polytetrafluoroethylene: polyvinylpyrrolidone is 100: 4: 5: (weight) ratio of 1, make thick 5 millimeters, wide 34 millimeters, high 50 millimeters square lithium ion battery A4.
Embodiment 5
This embodiment illustrates lithium ion anode material provided by the invention and contains the positive pole and the lithium ion battery of this positive electrode.
Method according to embodiment 1 prepares battery, be not both the acetylene black that conductive agent is surface area 1500 meters squared per gram, binding agent is that molecular weight is 400000 polytetrafluoroethylene (Japanese Wu Yu chemical industry), and dispersant is the polyvinylpyrrolidone (the occasion chemical industry is praised in Shanghai) of molecular weight 50000, presses LiFePO
4: acetylene black: polytetrafluoroethylene: polyvinylpyrrolidone is 100: 4: 5: 1 (weight) is than making thick 5 millimeters, wide 34 millimeters, high 50 millimeters square lithium ion battery A5.
Embodiment 6-10
Battery A1-A5 with the foregoing description 1-5 preparation, carry out the battery capacity test according to following method, battery is with 1CmA current charges to 3.8 volt under the normal temperature, after voltage rises to 3.8 volts with constant-potential charge, cut-off current is 0.05CmA, shelves 5 minutes, and battery is with 1CmA current discharge to 2.0 volt, shelved 5 minutes, the result is as shown in table 1.
Comparative Examples 2
With the battery CA1 of above-mentioned Comparative Examples 1 preparation, carry out the battery capacity test according to the described method of embodiment 6-10, the result is as shown in table 1.
Table 1
| The embodiment numbering | The battery numbering | Battery capacity (MAH) | The internal resistance of cell (megaohm) |
| Embodiment 6 | A1 | 738 | 41.2 |
| Comparative Examples 2 | CA1 | 620 | 78.5 |
| Embodiment 7 | A2 | 752 | 39.7 |
| Embodiment 8 | A3 | 741 | 42.6 |
| Embodiment 9 | A4 | 735 | 40.6 |
| Embodiment 10 | A5 | 701 | 51.3 |
As can be seen from Table 1, the battery A1-A5 that comprises the positive pole preparation that embodiment of the invention 1-5 provides, the battery CA1 of the positive pole preparation that provides with Comparative Examples 1 compares, battery capacity has improved respectively, 118 MAHs, 132 MAHs, 121 MAHs, 115 MAHs, 81 MAHs, the internal resistance of cell has reduced by 37.3 megaohms, 38.8 megaohms, 35.9 megaohms, 37.9 megaohms, 27.2 megaohms respectively, illustrate that anode provided by the invention is greatly improved the capacity of battery, the internal resistance of battery simultaneously significantly reduces.
Embodiment 11-15
Battery A1-A5 with the foregoing description 1-5 preparation, carry out the heavy-current discharge performance test according to following method, at ambient temperature, with the 1CmA electric current with battery charge to 3.8 volt, after voltage rises to 3.8 volts with constant-potential charge, cut-off current is 0.05CmA, shelves 5 minutes, obtains the capacity of battery normal temperature 0.2CmA current discharge to 2.0 volt; Repeat above-mentioned charge step again with the current discharge of battery with 3CmA and 5CmA, obtain the capacity of battery normal temperature 3CmA and 5CmA current discharge to 2.0 volt, the result is as shown in table 2.
Comparative Examples 3
With the battery CA of above-mentioned Comparative Examples 1 preparation, carry out the heavy-current discharge performance test according to the described method of embodiment 11-15, the result is as shown in table 2.
Table 2
| The embodiment numbering | The battery numbering | 3C/0.2C discharge ratio (%) | 5C/0.2C discharge ratio (%) |
| Embodiment 11 | A1 | 97.5 | 93.5 |
| Comparative Examples 3 | CA1 | 78.9 | 52.7 |
| Embodiment 12 | A2 | 98.4 | 94.0 |
| Embodiment 13 | A3 | 96.4 | 92.8 |
| Embodiment 14 | A4 | 97.0 | 93.0 |
| Embodiment 15 | A5 | 91.8 | 87.6 |
As can be seen from Table 2, the battery CA1 of the anode preparation that provides with Comparative Examples 1 compares, the battery A1-A5 of the anode preparation that embodiment of the invention 1-5 provides, the 3C/0.2C discharge ratio of battery has improved 23.6%, 24.7%, 22.1%, 22.9%, 16.3% respectively, 5C/0.2C the discharge ratio has improved 77.4%, 78.4%, 76.1%, 76.5%, 66.2% respectively, illustrates that anode provided by the invention makes the heavy-current discharge performance of battery obtain significantly improving.
Embodiment 16-20
Battery A1-A5 with the foregoing description 1-5 preparation, carry out the cycle performance test according to following method, at ambient temperature, with the 1CmA electric current with battery charge to 3.8 volt, after voltage rises to 3.8 volts,, be 0.05CmA, shelved 5 minutes by electric current with constant-potential charge, battery was shelved 5 minutes with 1CmA current discharge to 2.0 volt.Repeat above step 300 time, as a result shown in the table 3.
Comparative Examples 4
With the battery CA1 of above-mentioned Comparative Examples 1 preparation, carry out the cycle performance of battery test according to the described method of embodiment 16-20, the result is as shown in table 3.
Table 3
| The embodiment numbering | The battery numbering | Capacity sustainment rate (%) |
| Embodiment 16 | A1 | 92.6 |
| Comparative Examples 4 | CA1 | 62.0 |
| Embodiment 17 | A2 | 91.7 |
| Embodiment 18 | A3 | 93.4 |
| Embodiment 19 | A4 | 93.2 |
| Embodiment 20 | A5 | 90.3 |
As can be seen from Table 3, the battery CA1 of the anode preparation that provides with Comparative Examples 1 compares, the battery A1-A5 of the anode preparation that embodiment of the invention 1-5 provides, the capacity sustainment rate of battery has improved 49.3%, 47.9%, 50.6%, 50.3%, 45.6% respectively, illustrates that anode provided by the invention makes the cycle performance of battery obtain significantly improving.
Claims (10)
1. the positive electrode active materials of a lithium ion battery, this positive electrode active materials contains lithium metal phosphates, binding agent and conductive agent, it is characterized in that, this positive electrode active materials also contains dispersant, described dispersant is selected from polyacrylamide, the polypropylene acid esters, polyurethane, polyvinylpyrrolidone, polyisobutene succinimide, poly(ethylene oxide) ether, hydroxyethylcellulose, dodecyl poly(ethylene oxide) ester, fatty acid polyglycol oxirane ester, alkoxyl polyalkylene oxide acrylate, polycaprolactone, polystyrene-vinyl pyrrolidone, polystyrene-N, one or more in the N-divinyl acrylamide.
2. positive electrode active materials according to claim 1 wherein, is a benchmark with the amount of lithium metal phosphates, and the content of conductive agent is 1-15 weight %, and the content of binding agent is 1-20 weight %, and the content of dispersant is 0.1-5 weight %.
3. positive electrode active materials according to claim 1 wherein, is a benchmark with the amount of lithium metal phosphates, and the content of conductive agent is 2-10 weight %, and the content of binding agent is 2-15 weight %, and the content of dispersant is 0.2-2 weight %.
4. positive electrode active materials according to claim 1, wherein, described dispersant is a polyvinylpyrrolidone.
5. according to claim 1 or 4 described positive electrode active materials, wherein, described dispersant molecule amount is 1000-200000.
6. positive electrode active materials according to claim 1, wherein, described conductive agent is selected from one or more in acetylene black, superconduction carbon black, electrically conductive graphite, conductive carbon fibre, the metal dust.
7. according to claim 1 or 6 described positive electrode active materials, wherein, the specific area of described conductive agent is the 100-2000 meters squared per gram.
8. positive electrode active materials according to claim 1, wherein, described lithium metal phosphates has following molecular formula: LiMPO
4, wherein, M is selected from Fe, Mn, Co or Ni; Described binding agent is selected from one or more in Kynoar, polyvinyl alcohol, acid polyethylene butyral, polyacrylic acid formicester, carboxymethyl cellulose, methylcellulose, hydroxypropyl methylcellulose, the ethyl cellulose, and the molecular weight of described binding agent is 100000-2000000.
9. the positive pole of a lithium ion battery, this positive pole contain collector and coating and/or are filled in positive electrode active materials on the collector, and wherein, described positive electrode active materials is any described positive electrode active materials among the claim 1-8.
10. lithium rechargeable battery, this battery comprise battery container and are sealed in electrode group and electrolyte in this battery container; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that, the described positive pole of described just very claim 9.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102299335A (en) * | 2011-07-20 | 2011-12-28 | 彩虹集团公司 | Additive for lithium iron phosphate battery coating process |
| CN102340027A (en) * | 2011-09-21 | 2012-02-01 | 东莞市创明电池技术有限公司 | Lithium ion battery with high energy density |
| CN102403537A (en) * | 2011-11-30 | 2012-04-04 | 南京双登科技发展研究院有限公司 | Method for manufacturing lithium iron phosphate battery |
| CN103038925A (en) * | 2010-07-29 | 2013-04-10 | 原子能和代替能源委员会 | Electrode for a lithium battery |
| CN103199258A (en) * | 2013-03-07 | 2013-07-10 | 中航锂电（洛阳）有限公司 | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery |
| CN103392252A (en) * | 2011-02-23 | 2013-11-13 | 三洋电机株式会社 | Electrode for non-aqueous electrolyte secondary battery, method for producing same, and non-aqueous electrolyte secondary battery |
| CN106328989A (en) * | 2016-11-07 | 2017-01-11 | 上海碳源汇谷新材料科技有限公司 | Application of metal phosphate to negative electrode material of lithium-ion battery |
| CN107093724A (en) * | 2017-04-27 | 2017-08-25 | 柳州豪祥特科技有限公司 | The preparation method of anode material of lithium battery |
| CN108091847A (en) * | 2017-12-11 | 2018-05-29 | 北京国能电池科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| CN109817890A (en) * | 2019-01-25 | 2019-05-28 | 东莞市创明电池技术有限公司 | The preparation method of lithium ion battery positive electrode |
| CN109888184A (en) * | 2019-02-25 | 2019-06-14 | 天津艾克凯胜石墨烯科技有限公司 | A kind of graphene lithium ion battery flexibility anode thin film and preparation method thereof |
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| CN113725497A (en) * | 2021-09-03 | 2021-11-30 | 天能帅福得能源股份有限公司 | Preparation method of low-cost high-performance lithium ion battery using dispersing agent |
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| CN103038925A (en) * | 2010-07-29 | 2013-04-10 | 原子能和代替能源委员会 | Electrode for a lithium battery |
| CN103038925B (en) * | 2010-07-29 | 2015-07-29 | 原子能和代替能源委员会 | For the electrode of lithium battery |
| CN103392252A (en) * | 2011-02-23 | 2013-11-13 | 三洋电机株式会社 | Electrode for non-aqueous electrolyte secondary battery, method for producing same, and non-aqueous electrolyte secondary battery |
| CN102299335A (en) * | 2011-07-20 | 2011-12-28 | 彩虹集团公司 | Additive for lithium iron phosphate battery coating process |
| CN102340027A (en) * | 2011-09-21 | 2012-02-01 | 东莞市创明电池技术有限公司 | Lithium ion battery with high energy density |
| CN102340027B (en) * | 2011-09-21 | 2015-02-11 | 东莞市创明电池技术有限公司 | Lithium ion battery with high energy density |
| CN102403537A (en) * | 2011-11-30 | 2012-04-04 | 南京双登科技发展研究院有限公司 | Method for manufacturing lithium iron phosphate battery |
| CN103199258A (en) * | 2013-03-07 | 2013-07-10 | 中航锂电（洛阳）有限公司 | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery |
| CN103199258B (en) * | 2013-03-07 | 2016-06-22 | 中航锂电（江苏）有限公司 | Anode material for lithium-ion batteries, anode preparation method and lithium ion battery |
| CN106328989A (en) * | 2016-11-07 | 2017-01-11 | 上海碳源汇谷新材料科技有限公司 | Application of metal phosphate to negative electrode material of lithium-ion battery |
| CN107093724A (en) * | 2017-04-27 | 2017-08-25 | 柳州豪祥特科技有限公司 | The preparation method of anode material of lithium battery |
| CN107093724B (en) * | 2017-04-27 | 2020-06-19 | 柳州豪祥特科技有限公司 | Preparation method of lithium battery positive electrode material |
| CN108091847A (en) * | 2017-12-11 | 2018-05-29 | 北京国能电池科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery |
| US11999811B2 (en) | 2018-02-05 | 2024-06-04 | HYDRO-QUéBEC | Copolymers of ester and ether units, processes for producing same and uses thereof |
| CN112567548A (en) * | 2018-09-19 | 2021-03-26 | 株式会社村田制作所 | Secondary battery |
| CN109817890A (en) * | 2019-01-25 | 2019-05-28 | 东莞市创明电池技术有限公司 | The preparation method of lithium ion battery positive electrode |
| CN109888184A (en) * | 2019-02-25 | 2019-06-14 | 天津艾克凯胜石墨烯科技有限公司 | A kind of graphene lithium ion battery flexibility anode thin film and preparation method thereof |
| WO2020215316A1 (en) * | 2019-04-26 | 2020-10-29 | Dow Global Technologies Llc | Polyvinyl pyrollidone as a dispersant for lithium ion battery cathode production |
| CN111740177A (en) * | 2019-07-26 | 2020-10-02 | 瑞新材料科技(香港)有限公司 | Positive electrode material, positive electrode, battery, and battery pack |
| CN113725497A (en) * | 2021-09-03 | 2021-11-30 | 天能帅福得能源股份有限公司 | Preparation method of low-cost high-performance lithium ion battery using dispersing agent |
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