CN101577324A - Mixed type anode sizing agent of LiFePO4 battery and LiFePO4 battery using the anode sizing agent - Google Patents
Mixed type anode sizing agent of LiFePO4 battery and LiFePO4 battery using the anode sizing agent Download PDFInfo
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- CN101577324A CN101577324A CNA2009100990087A CN200910099008A CN101577324A CN 101577324 A CN101577324 A CN 101577324A CN A2009100990087 A CNA2009100990087 A CN A2009100990087A CN 200910099008 A CN200910099008 A CN 200910099008A CN 101577324 A CN101577324 A CN 101577324A
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- ferric phosphate
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Abstract
The invention relates to a mixed type anode sizing agent of a (lithium iron phosphate) LiFePO4 battery and a LiFePO4 battery using the anode sizing agent; the mixed type anode sizing agent of the LiFePO4 battery comprises the following components with parts by weight: 0.5 to 2 parts of LiFePO4, 0.5 to 2 parts of LiCoxNiyMnzO2, 0.05 to 0.3 part of conductive agent, 0.1 to 1.0 part of aqueous adhesive, 0.5 to 2 parts of deionized water and 0.05 to 0.25 part of polar solvent. The positive plate of the LiFePO4 battery is coated with aluminum foil of the mixed type anode sizing agent. The mixed type anode sizing agent of the LiFePO4 battery adopts the LiFePO4 material and LiMn1-x-yNixCoyO2 material for compatibility production, and the produced LiFePO4 battery has high power, low production cost, light weight, small volume, stable discharge plateau, low self-discharge, no memory effect and wide application.
Description
Technical field
The present invention relates to a kind of anode material of lithium battery and use the lithium battery of this positive electrode, relate in particular to a kind of ferric phosphate lithium cell mixed type anode sizing agent and use the ferric phosphate lithium cell of this anode sizing agent; Belong to technical field of lithium batteries.
Background technology
Lithium battery since commercialization, layered oxide LiCoO
2Positive electrode, capacity is higher, has extended cycle life, but the cobalt resource scarcity, costs an arm and a leg and have toxicity, therefore seeks the important research direction that excellent honest and clean, the dependable performance of price, eco-friendly positive electrode become lithium ion battery.LiNiO
2, LiNi
xCO
1-xLayered oxides such as O2 and with LiMn
2O
4For the spinel-type positive electrode of representing in the past decade obtains broad research, but, restricted their development prospect owing to its defective that exists separately.With olivine-type LiFePO
4Ferric phosphate lithium cell research causing numerous researchers' concern as positive electrode.
Ferric phosphate lithium cell is used for doing lithium rechargeable battery, and now main direction is an electrokinetic cell, relative NI-H, and the Ni-Cd battery has great advantage.Lithium iron phosphate dynamic battery seven big advantages: one, extra long life.Two, safe in utilization, LiFePO4 has solved the security hidden trouble of cobalt acid lithium and LiMn2O4 fully, cobalt acid lithium and LiMn2O4 can produce the life security of exploding to the consumer and constitute a threat under strong collision, even and LiFePO4 can not produce blast with the strict safety test of process yet in worst traffic accident.Three, electric current 2C fast charging and discharging greatly, under special charger, the 1.5C charging can make battery be full of in 40 minutes, and starting current can reach 2C, and lead-acid battery does not have this performance now.Four, high temperature resistant, LiFePO4 electric heating peak value can reach 350 ℃～500 ℃ and LiMn2O4 and cobalt acid lithium only about 200 ℃.Five, big capacity.Six, memory-less effect.Seven, environmental protection.But LiFePO
4The tap density of positive electrode is less, waits the volume of the ferric phosphate lithium cell of capacity to be greater than lithium ion batteries such as cobalt acid lithium, and its ion and electronic conductivity are not good, cause the charge-discharge magnification performance not good.This shortcoming has greatly influenced LiFePO
4Replace LiCoO
2Become anode material for lithium-ion batteries of new generation.
Chinese patent application (publication number: CN101183729A) relate to a kind of high capacity lithium iron phosphate power cell and manufacture craft thereof, this power battery anode material adopts LiFePO4, plus plate current-collecting body adopts aluminium foil, conductive agent is selected superconduction carbon black, electrically conductive graphite for use, the positive electrode binding agent is selected polyvinylidene fluoride for use, and negative material adopts natural or Delanium; Negative current collector adopts Copper Foil, and conductive agent is selected superconduction carbon black, electrically conductive graphite for use, and the negative material binding agent is selected polyvinylidene fluoride or CMC, butadiene-styrene rubber for use.The manufacture craft of this electrokinetic cell may further comprise the steps: batching, coating, baking, roll-in, film-making, baking, lamination, loam cake assembling, baking, fluid injection, change into, partial volume.Though the electrokinetic cell compact conformation that adopts above-mentioned manufacture craft and positive and negative pole material thereof to make, stable performance, thus battery capacity can improve greatly.But because the shortcoming of LiFePO 4 material self, its compacted density is lower, and the Capacity Ratio of working it out battery is lower, and power is less, understand discharge off in short time in use with the electrokinetic cell that single LiFePO 4 material is made as positive electrode, make troubles to the user.
Summary of the invention
The present invention is directed to the defective that prior art exists, provide that a kind of capacity is big, cost is low and all better ferric phosphate lithium cell mixed type anode sizing agent of specific capacity and specific energy aspect.
The objective of the invention is to realize by following technical proposal: a kind of ferric phosphate lithium cell mixed type anode sizing agent, this slurry comprise that the one-tenth of following weight portion is grouped into:
LiFePO
4: 0.5～2 part; LiCo
xNi
yMn
zO
2: 0.5～2 part;
Conductive agent: 0.05～0.3 part; Water-based binder: 0.1～1.0 part;
Deionized water: 0.5～2 part; Polar solvent: 0.05～0.25 part;
Wherein at LiCo
xNi
yMn
zO
2In, the number range of x is 1～5; The number range of y is 0.6～1.5; The number range of z is 0.6～1.5.Iron lithium phosphate (LiFePO
4) in lithium be positive monovalence; Central metal iron is positive divalence; Phosphate radical is negative trivalent, because the phosphate in the structure has stable effect to the framework of whole material, makes material itself have good thermal stability and cycle performance.LiFePO
4Mobility with one dimension direction, can be reversible in charge and discharge process deviate from and move into and be accompanied by the oxidation and the reduction of central metal iron.And LiFePO
4Theoretical capacitance be 170mAh/g, and have voltage platform 3.45V stably.At LiFePO
4The diffusion coefficient height of middle lithium ion, and LiFePO
4Through repeatedly discharging and recharging, olivine structural is still stable, and iron atom still is in octahedral site, can be as the good positive electrode of cycle performance.In charging process, iron atom is positioned at octahedral site, all is in the high-spin state.Though LiFePO4 has higher specific capacity and excellent high-temperature cycle performance and high security performance.But want cube little, in light weight for electrokinetic cell, discharge platform is stable, and self discharge is little, and capacity and power are big.And the electrical conductance of pure LiFePO 4 material and lithium ion diffusion are poor, thereby cause the high-rate battery discharge poor performance; The apparent density and the tap density of pure in addition LiFePO 4 material are lower, are difficult for processing, and the coating of anode sizing agent is difficulty relatively, and the battery capacity requirement that can't satisfy the high power capacity and the super high power of electrokinetic cell on the low side.And nickel-cobalt lithium manganate material energy density height all has excellent cyclical stability under normal temperature and high temperature; Stable circulation is reliable in 2.5～4.3/4.4V voltage range; Heat stability is good, stable＞300 ℃ of the material thermal decomposition under the 4.4V charged state, this material overcharging resisting performance is good in addition, specific area, apparent density and tap density are higher.But because nickel, two kinds of metal prices of cobalt are higher, so it is bigger to make lithium battery cost with it.And the present invention carries out the cost that compatibility had both been saved material with LiFePO 4 material and nickel-cobalt lithium manganate material, and have very high specific energy as the ferric phosphate lithium cell that positive electrode is made, be applicable to strict maximum weight and volume but require the demand of high-octane lithium iron phosphate dynamic battery.But LiFePO 4 material and nickel-cobalt lithium manganate material adopt common binder (as polyvinylidene fluoride, polytetrafluoroethylene etc.) to bond, and adhesive fastness is poor, and fatigue resistance is little, and suppleness is relatively poor, and is anti-oxidant, anti-reducing power a little less than.The present invention adopts the water-based binder to carry out the bonding problems such as adhesive fastness that can solve LiFePO 4 material and nickel-cobalt lithium manganate material.
In above-mentioned ferric phosphate lithium cell mixed type anode sizing agent, as preferably, this slurry comprises that the one-tenth of following weight portion is grouped into:
LiFePO
4: 0.8～1.5 part; LiCo
xNi
yMn
zO
2: 0.8～1.5 part;
Conductive agent: 0.1～0.25 part; Water-based binder: 0.5～0.8 part;
Deionized water: 0.8～1.5 part; Polar solvent: 0.1～0.2 part;
Wherein at LiCo
xNi
yMn
zO
2In, the number range of x is 2～4; The number range of y is 0.8～1.2; The number range of z is 0.8～1.2.The present invention is to above-mentioned composition and LiCo
xNi
yMn
zO
2Number range further optimize and restriction, by restriction with to optimize capacity, cost and specific capacity and the specific energy aspect of the ferric phosphate lithium cell mixed type anode sizing agent that obtains better.
In above-mentioned ferric phosphate lithium cell mixed type anode sizing agent, described conductive agent be in acetylene black, crystalline flake graphite and the conductive carbon black one or more.The weight of described relatively positive active material, the content of described conductive agent can be the content of conductive agent in the conventional lithium ion cell positive.Generally speaking, the content of described conductive agent is 0.05～0.3 part.Under the preferable case, the content of described conductive agent is 0.1～0.25 part, and the consumption that reduces conductive agent can improve battery capacity, and reduces cell thickness.The conductive carbon black that conductive carbon black of the present invention uses in can conventional ferric phosphate lithium cell.Under the preferable case, conductive carbon black of the present invention is 450～500 milliliters/100 grams for the DBP oil factor, and the mean particle diameter of described conductive carbon black is the 20-40 micron.When the DBP of described conductive carbon black oil factor in the above range the time, can further improve the discharge performance of ferric phosphate lithium cell.In addition, the mean particle diameter that suitably reduces conductive carbon black also can improve its conductivity.Described conductive carbon black all can be commercially available.In addition, described DBP oil factor is meant that 100 gram carbon blacks absorb volume (milliliter) number of dibutyl phthalate.Acetylene black of the present invention can be the acetylene black of using in the conventional ferric phosphate lithium cell.Described acetylene black can be commercially available.Under the preferable case, described acetylene black is that mean particle diameter is 20～50 microns a acetylene black.Crystalline flake graphite of the present invention can be the crystalline flake graphite that uses in the conventional ferric phosphate lithium cell.Described crystalline flake graphite can be commercially available.
In above-mentioned ferric phosphate lithium cell mixed type anode sizing agent, described water-based binder is a F-105 water-based binder.The present invention selects F-105 water-based binder for use, this water-based binder can well bond LiFePO4 and nickel-cobalt lithium manganate material, and it has the adhesive fastness height, and fatigue resistance is big, and suppleness is good, and is anti-oxidant, the characteristics that anti-reducing power is strong.Described F-105 water-based binder can be commercially available.
In above-mentioned ferric phosphate lithium cell mixed type anode sizing agent, described polar solvent is one or more in N-methyl pyrrolidone, dimethyl formamide, diethylformamide, dimethyl sulfoxide (DMSO), the oxolane.Positive electrode is being distributed in the polar solvent in the formed slurry system, because positive electrode and above-mentioned polar solvent all are the stronger materials of polarity, attraction to each other still exists, in order to reach better dispersion effect, under the preferable case, the polar solvent that the present invention adopts is the N-methyl pyrrolidone, and above-mentioned polar solvent can be commercially available.
Another object of the present invention is to provide a kind of ferric phosphate lithium cell, comprise housing, loam cake, lower cover, block, electrolyte and by the electric core unit that positive and negative plate and diaphragm paper are wound into, it is characterized in that: described positive plate is the aluminium foil that is coated with above-mentioned mixed type anode sizing agent.Make the thickness 0.015～0.025mm of positive plate aluminium foil in this ferric phosphate lithium cell, the viscosity of anode sizing agent is 1000～2000mPaS during coating, and the particle of anode sizing agent is less than 150 orders.Coated side density is 1.6g～1.7g/100cm2, in addition in order to accelerate the seepage velocity of electrolyte, makes the speeding up of electric core pole piece Electolyte-absorptive; Make the very easy technological standards scope that reaches of fluid injection; Reduced the digestion time of electric core after the fluid injection; Shortened the production cycle of battery; Reduced the defective products rate of electric core; Improved the cycle performance of battery; As being provided with permeability hole on positive plate in the electric core unit and the negative plate.The electrolyte that this ferric phosphate lithium cell adopts is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the electrolyte of this area routine.Be selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more such as electrolyte reason salt.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.This ferric phosphate lithium cell septation paper is arranged between positive plate and the negative plate, has electrical insulation capability and liquid retainability energy.Described diaphragm paper can be selected from and well known to a person skilled in the art various diaphragm papers used in the ferric phosphate lithium cell, for example polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper etc.
The structure of this ferric phosphate lithium cell is the existing common structure of lithium battery, and described loam cake directly passes through seal welding with block, also is provided with liquid injection hole and airtight construction on the described block.Described electric core unit posts the gummed paper that is provided with permeability hole perpendicular to the upper end of its coiling direction.The diameter of described permeability hole is 0.8～1mm.Described housing adopts stainless steel material to make.
In above-mentioned ferric phosphate lithium cell, described negative plate is the Copper Foil that is coated with negative material, and described negative material is grouped into by the one-tenth of following weight portion:
Graphite: 0.5～2 part; Conductive agent: 0.01～0.1 part;
Negative pole binding agent: 0.1～0.3 part; Deionized water: 1～2 part;
Solvent: 0.05～0.15 part.
Make the thickness 0.010～0.015mm of negative plate Copper Foil in this ferric phosphate lithium cell, the viscosity of negative material is 1500～2500mPaS during coating, and the particle of anode sizing agent is less than 120 orders.Coated side density is 0.70g～1.0g/100cm2.
In above-mentioned ferric phosphate lithium cell, described conductive agent is a kind of in nickel powder, the conductive carbon black.
In above-mentioned ferric phosphate lithium cell, described negative pole binding agent is made up of in hydrophilic agglomerant and the hydrophobicity binding agent one or both, described hydrophilic agglomerant is one or more in sodium carboxymethylcellulose, carboxyethyl cellulose, the polyvinyl alcohol, and described hydrophobicity binding agent is one or both in polytetrafluoroethylene, the butadiene-styrene latex.
In above-mentioned ferric phosphate lithium cell, described solvent is N-methyl pyrrolidone, acetone, N, one or more in the dinethylformamide.
Negative pole described in this lithium battery adopts known negative pole in this area, promptly contains negative plate and the negative electrode material layer that is coated on this negative plate.Described negative electrode material layer comprises graphite, binding agent and conductive agent etc.Described binding agent can be the various binding agents that are used for the ferric phosphate lithium cell negative pole in the prior art, preferred described negative pole binding agent is made up of hydrophilic agglomerant and hydrophobicity binding agent, both weight ratios are 0.5: 1～2: 1, described hydrophilic agglomerant is one or more in sodium carboxymethylcellulose, carboxylic propyl group, carboxyethyl cellulose, the polyvinyl alcohol, and described hydrophobicity binding agent is one or both in polytetrafluoroethylene, the butadiene-styrene latex.Negative material provided by the invention also comprises conductive agent.Because conductive agent is used to increase the conductivity of electrode, reduce the internal resistance of battery, the content of described conductive agent and kind are conventionally known to one of skill in the art, for example, are benchmark with the negative material, the content of conductive agent is generally 0.1～7 weight %.Described conductive agent can be selected from one or both in conductive carbon black, the nickel powder.Described solvent is N-methyl pyrrolidone, acetone, N, one or more in the dinethylformamide.Above-mentioned negative material can be commercially available.
In sum, the present invention has the following advantages:
1, to adopt LiFePO 4 material and nickel-cobalt lithium manganate material to carry out battery specific capacity and specific energy aspect that compatibility produces better for ferric phosphate lithium cell mixed type anode sizing agent of the present invention, the power height, and long service life, manufacturing cost is low.
2, ferric phosphate lithium cell of the present invention is in light weight, and volume is little, and discharge platform is stable, and self discharge is little, and memory-less effect is of many uses, and security performance is good.
Description of drawings
Fig. 1 is the perspective view of ferric phosphate lithium cell of the present invention.
Fig. 2 is the ferric phosphate lithium cell process chart that the present invention produces.
Fig. 3 is the ferric phosphate lithium cell performance test data cycle-index figure that the present invention produces.
Among the figure, 1, housing; 2, positive plate; 3, negative plate; 4, permeability hole; 5, electric core unit.
Embodiment
Below by specific embodiment also in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail; But the present invention is not limited to these embodiment.
As shown in Figure 1, this ferric phosphate lithium cell, comprise housing 1, loam cake, lower cover, block, electrolyte and the electric core unit 5 that is wound into by positive and negative plate 3 and diaphragm paper, cover down and be provided with explosion-proof relief mechanism, be provided with permeability hole 4 on positive plate 2 in the electric core unit 5 and the negative plate 3.
Directly pass through seal welding at loam cake and block, also be provided with liquid injection hole and airtight construction on the described block.Electricity core unit 5 posts the gummed paper that is provided with permeability hole 4 perpendicular to the upper end of its coiling direction.The diameter of the permeability hole 4 in the present embodiment is 1mm.The housing 1 of this ferric phosphate lithium cell adopts stainless steel material to make.
Shown in the technological process of production figure that Fig. 2 produces ferric phosphate lithium cell, mixed 5～10 hours according to the positive electrode of embodiment in the table 11, the viscosity of anode sizing agent is 1500 ± 500mPaS behind the batch mixing, the particle of anode sizing agent is less than 150 orders.Negative material according to embodiment in the table 21 mixed 5～10 hours, and the viscosity of cathode size is 2000 ± 500mPaS behind the batch mixing, and the particle of cathode size is less than 120 orders.
Selection thickness is 0.018 ± 0.002mm, and width is the pure aluminum foil of 410 ± 2.0mm, with the solvent evaporation of the anode sizing agent of baking oven after with batch mixing, is coated on the pure aluminum foil under constant temperature is 20 ℃ condition then, and coated side density is 1.650 ± 0.020g/100cm
2, coating width is 406 ± 2mm.Selection thickness is 0.012 ± 0.002mm, and width is two light Copper Foils of 420 ± 2.0mm, with the solvent evaporation of the cathode size of baking oven after with batch mixing, is coated on the Copper Foil under constant temperature is 30 ℃ condition then, and coated side density is 0.890 ± 0.015g/100cm
2, coating width is 416 ± 2mm.
The positive maximum roll film that is coated with anode sizing agent put into charge into nitrogen, temperature is 105 ± 5 ℃, and vacuum degree was toasted 10～15 hours in the baking oven of-0.085 ± 0.010MPaS, wherein for anti-oxidation, in baking oven, charge and discharge nitrogen one time in per 3 hours, and required purity 〉=99.5% of nitrogen.The negative maximum roll film that is coated with cathode size put into charge into nitrogen, temperature is 110 ± 5 ℃, and vacuum degree was toasted 10～12 hours in the baking oven of-0.085 ± 0.010MPaS, wherein for anti-oxidation, in baking oven, charge and discharge nitrogen one time in per 3 hours, and required purity 〉=99.5% of nitrogen.
It is that 50～100 tons flaking machine rolls sheet that positive maximum roll film after the above-mentioned baking and negative maximum roll film are placed on pressure, and anodal rolling thickness is 0.165 ± 0.003mm, and the negative pole rolling thickness is 0.102 ± 0.003mm, carries out cut-parts after rolling sheet.
After the cut-parts sheet positive and negative pole pieces is cut into the positive and negative plate of strip, wherein positive plate is of a size of length * wide=(976 ± 2) * (56.5 ± 0.2) mm; Negative plate is of a size of length * wide (1035 ± 2) * (58.0 ± 0.2) mm.Guarantee that wherein positive and negative plate does not have burr, the edge does not have bending.With ultrasonic wave electric welding machine spot welding aluminum strip in the middle part of positive plate, the specification of aluminum strip is thickness * width * length=0.10 * 4.0 * 73.0mm, clap after the ultrasonic spot welding and paste common dark brown high tempreture tape on aluminum strip, wherein the specification of dark brown high tempreture tape is width * length=8.0 * 68.0mm.Form two lugs with the ultrasonic wave electric welding machine at negative plate two ends spot welding nickel bar, the nickel bar specification that wherein forms lug one is thickness * width * length=0.07 * 3.0 * 65.0mm, the nickel bar specification that forms lug two is thickness * width * length=0.10 * 4.0 * 71.0mm, ultrasonic spot welding is clapped and the common dark brown high tempreture tape of subsides on the nickel bar after forming lug, the specification of wherein dark brown high tempreture tape one is width * length=12.0 * 59.0mm, and the specification of dark brown high tempreture tape two is width * length=12.0 * 63.0mm.
The above-mentioned positive and negative plate that is made put into charge into nitrogen, temperature is 90 ± 5 ℃, and vacuum degree was toasted 1～3 hour in the baking oven of-0.085 ± 0.010MPaS, wherein for anti-oxidation, requires purity 〉=99.5% of nitrogen.The baking back is brushed sheet respectively to positive and negative plate, adopt half-automatic winder to reel after the vacuum cleaning, wherein positive plate is last, negative pole is following, the centre is provided with diaphragm paper, and wherein the specification of diaphragm paper is thickness * width=0.020 * 60.0mm, and the back of reeling is carried out vacuum cleaning to the volume core and detected the whether short circuit of volume core, load onto down insulation spacer then, and roll lug well.To roll up core then and pack in the box hat, be that the high-frequency welder of 9.5～15Hz welds in the box hat bottom with the negative lug frequency, requires firm welding during welding, and no rosin joint does not have obviously weldering and prints.For the ease of block, the ferric phosphate lithium cell blank is carried out slot rolling, wherein neck depth is 3.65～3.80mm, the internal diameter specification is 14.20 ± 0.10mm, following section highly is 60.90 ± 0.10mm, and external diameter is smaller or equal to 18.10mm, and the box hat total height is 66.30 ± 0.10mm, adopt vacuum cleaning behind the slot rolling, inhale the metal fragment that produces when removing slot rolling.
Ferric phosphate lithium cell blank behind the above-mentioned slot rolling put into charge into nitrogen, temperature is 80 ℃～90 ℃, and vacuum degree was toasted 45～50 hours in the baking oven of-0.085 ± 0.010MPaS, wherein for anti-oxidation, requires purity 〉=99.995% of nitrogen.Common lithium battery electrolytes is injected in baking back, needs to survey whether short circuit of battery before the fluid injection, adopts the mode that vacuumizes to inject the electrolyte in the battery blank, and reservoir quantity is 10.2 ± 0.10g, fluid injection at twice.After the fluid injection by laser welder just the aluminium strip on the positive plate and block connect together and block sealed, aluminium strip is welded on requires no rosin joint when block is gone up, do not have and turn black no burn-through.Carry out forming and capacity dividing after sealing, formation process must disposablely be finished incessantly, can not arbitrarily end midway or stop to change into curve to answer smooth binding, electric current should be controlled at 0.05C/30 minute, 0.1C/120 minute, 0.2C/360 minute, transfer constant voltage after constant current is full of to and continue to fill, must disposable abundance.The every index of electrical property is all met the battery of technological requirement and battery that every electrical performance indexes end reaches technological requirement is put warehouse-in respectively.
Embodiment 2～5
Negative material according to embodiment 2～5 in the positive electrode of embodiment in the table 1 2～5 and the table 2 carries out batch mixing, and other technological process repeats no more with embodiment 1.
The positive electrode weight proportion (kg) of table 1: embodiment 1～5 ferric phosphate lithium cell
The LiCo described in the embodiment 1 wherein
xNi
yMn
zO
2The numerical value of middle x is 1, and the numerical value of y is 1.5, and the number range of z is 0.8, wherein LiCo1Ni
1.5Mn
0.8O
2The water content of material is 0.060wt%, and specific area is 0.55m
2/ g, apparent density is 1.1g/cm
3, tap density is 2.46g/cm
3, the D10 granularity is 3.02 μ m, and the D50 granularity is 8.97 μ m, and the D90 granularity is 18.55 μ m; Described conductive agent is an acetylene black; Described polar solvent is the N-methyl pyrrolidone.
LiCo described in the embodiment 2
xNi
yMn
zO
2The numerical value of middle x is 2, and the numerical value of y is 1.2, and the number range of z is 1.0, wherein LiCo
2Ni
1.2Mn
1.0O
2The water content of material is 0.080wt%, and specific area is 0.43m
2/ g, apparent density is 1.2g/cm
3, tap density is 2.34g/cm
3, the D10 granularity is 3.04 μ m, and the D50 granularity is 9.12 μ m, and the D90 granularity is 18.65 μ m; Described conductive agent is a crystalline flake graphite; Described polar solvent is a dimethyl formamide.
LiCo described in the embodiment 3
xNi
yMn
zO
2The numerical value of middle x is 3, and the numerical value of y is 1.0, and the number range of z is 1.2, wherein LiCo
3Ni
1.0Mn
1.2O
2The water content of material is 0.050wt%, and specific area is 0.35m
2/ g, apparent density is 1.0g/cm
3, tap density is 2.52g/cm
3, the D10 granularity is 3.03 μ m, and the D50 granularity is 9.02 μ m, and the D90 granularity is 18.42 μ m; Described conductive agent is a conductive carbon black; Described polar solvent is a diethylformamide.
LiCo described in the embodiment 4
xNi
yMn
zO
2The numerical value of middle x is 4, and the numerical value of y is 0.8, and the number range of z is 1.5, wherein LiCo
4Ni
0.8Mn
1.5O
2The water content of material is 0.060wt%, and specific area is 0.54m
2/ g, apparent density is 1.12g/cm
3, tap density is 2.18g/cm
3, the D10 granularity is 3.03 μ m, and the D50 granularity is 8.98 μ m, and the D90 granularity is 18.36 μ m; Described conductive agent is conductive carbon black and crystalline flake graphite, and weight ratio between the two is 8: 6; Described polar solvent is a dimethyl sulfoxide (DMSO).
LiCo described in the embodiment 5
xNi
yMn
zO
2The numerical value of middle x is 5, and the numerical value of y is 0.6, and the number range of z is 0.6, wherein LiCo
5Ni
0.6Mn
0.6O
2The water content of material is 0.045wt%, and specific area is 0.38m
2/ g, apparent density is 1.1g/cm
3, tap density is 2.51g/cm
3, the D10 granularity is 3.05 μ m, and the D50 granularity is 9.06 μ m, and the D90 granularity is 18.46 μ m; Described conductive agent is conductive carbon black and crystalline flake graphite, and weight ratio between the two is 5: 5; Described polar solvent is an oxolane.
The negative material weight proportion (kg) of table 2: embodiment 1～5 ferric phosphate lithium cell
Wherein the conductive agent described in the embodiment 1 is a nickel powder; Described negative pole binding agent is made up of hydrophilic agglomerant and hydrophobicity binding agent, and both weight ratios are 0.5: 1, and described hydrophilic agglomerant is a carboxyethyl cellulose, and described hydrophobicity binding agent is a polytetrafluoroethylene; Described solvent is the N-methyl pyrrolidone.
Conductive agent described in the embodiment 2 is a conductive carbon black; Described negative pole binding agent is made up of hydrophilic agglomerant and hydrophobicity binding agent, and both weight ratios are 1: 1, and described hydrophilic agglomerant is a polyvinyl alcohol, and described hydrophobicity binding agent is a butadiene-styrene latex; Described solvent is an acetone.
Conductive agent described in the embodiment 3 is a nickel powder; Described negative pole binding agent is made up of hydrophilic agglomerant and hydrophobicity binding agent, and both weight ratios are 1.5: 1, and described hydrophilic agglomerant is a sodium carboxymethylcellulose, and described hydrophobicity binding agent is a butadiene-styrene latex; Described solvent is N, dinethylformamide.
Conductive agent described in the embodiment 4 is a conductive carbon black; Described negative pole binding agent is a sodium carboxymethylcellulose; Described solvent is the N-methyl pyrrolidone.
Conductive agent described in the embodiment 5 is a conductive carbon black; Described negative pole binding agent is that the negative pole binding agent is made up of hydrophilic agglomerant and hydrophobicity binding agent, and both weight ratios are 2: 1, and described hydrophilic agglomerant is a sodium carboxymethylcellulose, and described hydrophobicity binding agent is a butadiene-styrene latex; Described solvent is the N-methyl pyrrolidone.
Randomly draw the ferric phosphate lithium cell sample that embodiment 1～5 makes, the battery performance to its different cycle-indexes under constant voltage charge and constant-current discharge state detects, and testing result is shown in Fig. 3, table 3 and table 4.
Table 3: the battery performance of different cycle-indexes under this ferric phosphate lithium cell sample constant voltage charge state
| Cycle-index | Set electric current (mA) | Setting voltage (V) | Starting voltage (V) | Final voltage (V) | Termination capacity (mAh) |
| 1 | 550 | 3.650 | 3.163 | 3.650 | 1023.811 |
| 101 | 550 | 3.650 | 3.155 | 3.650 | 940.906 |
| 201 | 550 | 3.650 | 3.175 | 3.650 | 893.230 |
| 301 | 550 | 3.650 | 3.196 | 3.650 | 862.095 |
| 401 | 550 | 3.650 | 3.203 | 3.650 | 841.851 |
| 501 | 550 | 3.650 | 3.209 | 3.650 | 804.072 |
| 601 | 550 | 3.650 | 3.208 | 3.650 | 784.861 |
| 701 | 550 | 3.650 | 3.204 | 3.650 | 764.996 |
| 801 | 550 | 3.650 | 3.204 | 3.650 | 743.126 |
Table 4: the battery performance of different cycle-indexes under this LiFePO4 sample constant-current discharge state
| Cycle-index | Set electric current (mA) | Setting voltage (V) | Starting voltage (V) | Final voltage (V) | Termination capacity (mAh) |
| 1 | 11000.000 | 2.000 | 2.905 | 1.998 | 959.673 |
| 101 | 11000.000 | 2.000 | 2.855 | 1.933 | 941.111 |
| 201 | 11000.000 | 2.000 | 2.765 | 1.996 | 886.595 |
| 301 | 11000.000 | 2.000 | 2.847 | 1.956 | 861.663 |
| 401 | 11000.000 | 2.000 | 2.858 | 1.965 | 837.062 |
| 501 | 11000.000 | 2.000 | 2.848 | 1.983 | 806.667 |
| 601 | 11000.000 | 2.000 | 2.812 | 1.947 | 782.364 |
| 701 | 11000.000 | 2.000 | 2.788 | 1.963 | 764.176 |
| 801 | 11000.000 | 2.000 | 2.795 | 1.981 | 747.844 |
From Fig. 3, table 3, table 4 as can be seen: this ferric phosphate lithium cell is in light weight, and volume is little, and discharge platform is stable, and self discharge is little, and memory-less effect is of many uses, and security performance is good.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific embodiments as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (10)
1, a kind of ferric phosphate lithium cell mixed type anode sizing agent, this slurry comprises that the one-tenth of following weight portion is grouped into:
LiFePO
4: 0.5～2 part; LiCo
xNi
yMn
zO
2: 0.5～2 part;
Conductive agent: 0.05～0.3 part; Water-based binder: 0.1～1.0 part;
Deionized water: 0.5～2 part; Polar solvent: 0.05～0.25 part;
Wherein at LiCo
xNi
yMn
zO
2In, the number range of x is 1～5; The number range of y is 0.6～1.5; The number range of z is 0.6～1.5.
2, ferric phosphate lithium cell mixed type anode sizing agent according to claim 1 is characterized in that: this slurry comprises that the one-tenth of following weight portion is grouped into:
LiFePO
4: 0.8～1.5 part; LiCo
xNi
yMn
zO
2: 0.8～1.5 part;
Conductive agent: 0.1～0.25 part; Water-based binder: 0.5～0.8 part;
Deionized water: 0.8～1.5 part; Polar solvent: 0.1～0.2 part;
Wherein at LiCo
xNi
yMn
zO
2In, the number range of x is 2～4; The number range of y is 0.8～1.2; The number range of z is 0.8～1.2.
3, ferric phosphate lithium cell mixed type anode sizing agent according to claim 2 is characterized in that: described conductive agent be in acetylene black, crystalline flake graphite and the conductive carbon black one or more.
4, ferric phosphate lithium cell mixed type anode sizing agent according to claim 3 is characterized in that: described water-based binder is a F-105 water-based binder.
5, ferric phosphate lithium cell mixed type anode sizing agent according to claim 4 is characterized in that: described polar solvent is one or more in N-methyl pyrrolidone, dimethyl formamide, diethylformamide, dimethyl sulfoxide (DMSO), the oxolane.
6, a kind of ferric phosphate lithium cell, comprise housing, loam cake, lower cover, block, electrolyte and by the electric core unit that positive and negative plate and diaphragm paper are wound into, it is characterized in that: described positive plate is the aluminium foil that is coated with any described mixed type anode sizing agent of claim 1～5.
7, ferric phosphate lithium cell according to claim 6 is characterized in that: described negative plate is the Copper Foil that is coated with negative material, and described negative material is grouped into by the one-tenth of following weight portion:
Graphite: 0.5～2 part; Conductive agent: 0.01～0.1 part;
Negative pole binding agent: 0.1～0.3 part; Deionized water: 1～2 part;
Solvent: 0.05～0.15 part.
8, ferric phosphate lithium cell according to claim 7 is characterized in that: described conductive agent is a kind of in nickel powder, the conductive carbon black.
9, according to claim 7 or 8 described ferric phosphate lithium cells, it is characterized in that: described negative pole binding agent is made up of in hydrophilic agglomerant and the hydrophobicity binding agent one or both, described hydrophilic agglomerant is one or more in sodium carboxymethylcellulose, carboxyethyl cellulose, the polyvinyl alcohol, and described hydrophobicity binding agent is one or both in polytetrafluoroethylene, the butadiene-styrene latex.
10, according to claim 7 or 8 described ferric phosphate lithium cells, it is characterized in that: described solvent is N-methyl pyrrolidone, acetone, N, one or more in the dinethylformamide.
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