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28Cathode Manufacture for Lithium-Ion BatteriesJianlin Li, Claus Daniel, and David L. Wood III

28.1Introduction

As the most promising• energy source for portable electronics, lithium-ion batteriesQ1have attracted much attention in the last two decades. Extensive work has been doneto develop novel materials, especially cathodes. As described in the Chapter 12 inthis book, LiCoO2 [1–15], LiMn2O4 [16–20], and LiFePO4 [21–25] are typical cathodematerials. Compared with LiCoO2, LiMn2O4, of the spinel mineral group, is cheaperand easier to synthesize [26]. It has excellent rate capability, high thermal stability,and acceptable environmental compatibility [25]. On the other hand, it has lowdischarge capacity and shows significant capacity fading during charge–dischargecycling [27]. It has been postulated that the capacity fading is caused by Jahn–Tellerdistortion of Mn3+ [28], Mn2+ dissolution [29], and electrolyte decomposition onthe electrode [30, 31]. Jahn–Teller distortion is due to the reduction of the averageoxidation state of Mn during lithium intercalation, which can lead to a structuredistortion from cubic LiMn2O4 to tetragonal Li2Mn2O4. LiFePO4, which has theolivine structure, is nontoxic and has excellent cycle stability. It has moderatecapacity [32], shows smaller volume change during intercalation, and exhibitssmaller charge–discharge heat flow than other cathode materials [25]. However,the electrical conductivity is relatively poor, on the order of 10−9 S cm−1 at roomtemperature [33]. Although LiCoO2 has some disadvantages, such as cost, toxicity,and harmfulness to the environment, it is the most widely commercially usedmaterial [26, 34] because of its high operating voltage, high specific capacity, andlong cycle life.

Great efforts have been made in electrolyte development to achieve desirablelithium-ion conductivity, dielectric constant, viscosity, and thermal stability. Thesolvent systems include single solvent [35, 36] and cosolvent [37–44]. A mix-ture of ethylene carbonate (EC) and dimethyl carbonate/ethyl methyl carbonate(DMC/EMC) has been widely adopted by researchers and manufacturers [45–48].LiPF6 is the preferred salt due to its overall performance [49]. An overview ofelectrolyte development is provided by Ahmad [49], and electrolyte processing hasalso been discussed elsewhere [50]. In addition, the introduction of lithium-ion

Handbook of Battery Materials, Second Edition. Edited by Claus Daniel and Jurgen O. Besenhard. 2011 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2011 by Wiley-VCH Verlag GmbH & Co. KGaA.

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938 28 Cathode Manufacture for Lithium-Ion Batteries

batteries to large formats has been delayed by the flammability of electrolytes. Inthe past decade, efforts have been made to decrease electrolyte flammability andto improve the thermal stability of electrodes including adding flame retardants[51–57]. The topic of battery performance as related to flame retardants has beenaddressed elsewhere [50]. Separator materials have also been summarized by Aroraet al. [58].

It has been reported that particle properties, including particle size [21, 59, 60],size distribution [61], crystallite size [26], and particle shape [62], have significantinfluence on cathode performance during operation. In addition, the developmentof lithium-ion batteries with high charge and discharge rate capability seems tobe limited by the rate performance of cathode materials [63]. Different methodshave been tried to improve the rate performance of cathode materials, includingthe addition of oxide coatings [64–69] and conductive substances including carbon[70–72] or metal powder [7, 73]. An overview can also be found in Ref. [50]. Thischapter will focus on cathode processing and fabrication.

28.2Electrode Manufacture

There are two typical cathodes: composite cathodes and thin-film cathodes. Com-posite cathodes are fabricated by a process of casting, coating, or printing slurries.Fabrication of thin-film cathodes usually involves vacuum techniques.

28.2.1Slurry Processing

Composite cathodes consist of active materials, binders, and conductive additives.These components are mixed into a slurry before casting or printing onto acurrent collector. According to the type of solvent used, the processing of electrodescan be classified into two categories: (i) an organic solvent-based (nonaqueous)system and (ii) a water-based (aqueous) system [74]. In conventional lithium-ionbattery processing, flammable organic solvents are typically used to obtain a stablesuspension. Typically, polyvinylidene fluoride (PVDF) and N-methyl-2-pyrrolidone(NMP) are the binder and solvent, respectively. However, this nonaqueous systemresults in both cost and safety concerns [75, 76]. Recently, attempts have beenmade to use an aqueous system [42, 77], since it poses less of an environmentalhazard and is less costly. However, the powders tend to agglomerate in the aqueoussuspension, which is ascribed to strong hydrogen bonding and electrostatic forces[78]. Therefore, one key issue in implementing aqueous systems is to control theagglomeration, which can improve the dispersion and stability of the slurries.Slurries in both aqueous and nonaqueous system can be deposited on substratesby casting, printing, or coating processes.

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28.2.1.1 CastingDoctor blade methods have been used for fabricating laboratory scale samples byapplying cathode slurry coatings onto current collectors. Refined techniques forfabricating large scale cathodes based on tape casting and slot-die coating, methodscurrently used in industry, are under development at Oak Ridge National Laboratory(ORNL). The effects of processing parameters, including slurry formulation anddrying conditions, on the porosity, pore structure, pore size distribution, andelectrochemical performance of cathodes are being investigated.

28.2.1.1.1 Tape Casting Tape casting has long been used in industry forfabricating many types of parts from ceramic slurries. Tape casting was firstdescribed in the 1940s by Glen Howatt [79], who is regarded as the ‘father’ ofthe process, which is advantageous in producing large-area, thin, flat ceramic, ormetallic parts [80]. It can be used to produce films as thin as 5 µm, while the typicaldried thickness is from 25 to 1270 µm [80].

A tape caster consists of a stationary doctor blade, a moving carrier, and a dryingzone. In a typical tape casting process for producing cathodes for lithium-ionbatteries, the cathode slurry is poured into a reservoir behind the doctor blade andthen cast on a moving aluminum foil carrier. A schematic of a tape casting processis shown in Figure 28.1. The wet thickness of the cathode tape is defined as the gapbetween the doctor blade and the Al foil. Additional factors also affect the thicknessof the tape, including the viscosity of the slurry, the reservoir depth, the speedof movement of the aluminum foil, and the shape of the doctor blade [80]. Afterthe wet cathode tape is cast, it is moved to a drying process where the solventsare evaporated from the surface, and a pre-dried tape is produced on the foil. Thepre-dried tape is usually transferred to a vacuum oven for further drying.

The performance of cathodes is highly affected by the slurry properties anddrying methods. Viscosity is one of the most important properties of slurries. Itis determined by the slurry composition, including the choice of solvents, thesolvent concentration, the properties of active material particles, the choice andconcentration of binders, the choice and concentration of carbon blacks, and thesolids loading. It is also affected by additional factors, including mixing sequence,mixing time, and de-aeration processes.

PVDF and NMP are the typical binder and solvent, respectively. The use ofvarious carbon blacks can also be found in the literature. The typical mass of activematerials, binder, and carbon black in dry components ranges from 75 to 90%, 5

Doctor blade

Heating element

Green tape

Aluminum foil

Figure 28.1 Schematic of tape casting.

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940 28 Cathode Manufacture for Lithium-Ion Batteries

to 10%, and 5 to 15%, respectively. The ratio of NMP to dry materials ranges from2 to 10 mL g−1 and has been reported in Ref. [81]. The properties of the particlesof the active material, including particle size, size distribution, and surface area,also affect the slurry viscosity. A shear-thinning property is often desirable forslurries, so that when the slurries pass under a doctor blade, they will display alower viscosity under the shear of the blade and a higher viscosity downstreamfrom the blade. This prevents the slurries from spreading out of the cast region.The viscosity of the slurries may also increase over time under no shear (knownas thixotropy). This is due to short-range order forming of the polymer network.Common methods to combat thixotropy include storing the slurries under shearor avoiding extended storage time between de-aeration and casting [80].

After the slurries are cast, they need to be dried. There are two major mechanismsin the drying process: (i) NMP evaporation from the surface of the tape and (ii) NMPdiffusion through the tape to the drying surface. Diffusion through the tape is themost likely rate-limiting step [80]. NMP evaporation from the surface depends onthe concentration of NMP vapor in the local atmosphere, the local air temperature,and the NMP temperature. The diffusion rate through the tape is affected by thebinder concentration, particle size, wet tape temperature, and so on. Ideally, theNMP concentration should be uniform throughout the tape during drying so thatthe entire tape dries at the same rate. It has also been pointed out that the fastestway to dry a tape is to heat the bottom of the tape without heating the air. Thisenhances the solvent mobility in the tape [80].

28.2.1.1.2 Slot-Die Coating Slot-die coating was invented by Beguin [82] andis considered a fast and precise means for the manufacture of photographic filmand papers. It has recently been applied to batteries [83]. In slot-die coating ofcomposite cathodes for lithium-ion batteries, the coating is squeezed out from areservoir through a slot-die by gravity or under hydraulic ‘pump’ pressure onto amoving aluminum foil. The slot has generally a much smaller cross-section thanthat of the reservoir, and is typically oriented perpendicular to the direction ofaluminum foil movement. The deposited cathode films must also be uniform anddefect-free. A schematic of slot-die coating is shown in Figure 28.2. Successfuloperation depends on the stability of the coating bead that fills the gap between theslot-die and the aluminum foil. The coating speed can be increased by applyingvacuum underneath the coating bead [84]. This deposition method is contactless

Heating elementAl foil

Coating beadSlot die

shim

Slurryinlet

Vacuum adjustment Coating roll

Roller

Figure 28.2 Schematic of slot-die coating.

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because there is no doctor blade resting on the substrate, and it generates noadditional tensile stress in the substrate foil.

There are three basic slot-die orientations: die facing upward, horizontal, anddownward. With the die face pointing upward, coating can be problematic, es-pecially with thin or low-viscosity slurries, since slurries can flow backwardsdown the web toward the die. The tendency for slurries to back flow on theweb can be reduced by changing the orientation of the die to either horizontalor facing downward. The horizontal position also provides the best combinationof air purging at start-up, clean operation, and the finest degree of operatoradjustment.

One advantage of slot-die coating is the low contamination of the coating layer.The entire slurry flow path is sealed against the environment until the slurryreaches the aluminum foil. Wear in a slot-die system is also very low in comparisonto most other coating methods. This further reduces contamination of a coatedproduct.

Another advantage of the slot-die coating process is that the coating thickness isdetermined by flow rate and web speed rather than gap thickness. Consequently,emphasis on the slot-die coating process has been on finding a stable operatingregion within which a uniform and defect-free coating is possible [84]. Ruschak hasperformed significant development of the slot-die coating process [85]. He definesthe coating bead as the liquid contained within the upstream and downstreammenisci, that is, formed between the die head and the substrate. The shapeand the stability of the coating bead has a significant role in determining theoptimum operating coating parameters [86]. Lee and co-workers have also studiedthe lower coating limit in the slot-die coating process [87]. They pointed out thatthe higher viscosity would decrease the maximum operational coating speed. Theminimum coating thickness is also related to capillary number (Ca). The thicknessis proportional to a low value of Ca, but it approaches a constant of approximately0.6–0.7 times the coating gap at high values of Ca. The critical capillary number(Ca∗) is defined by the transition point between these two regions.

Air entrainment can take place during the process, and this depends on severalfactors. According to Deryagin and Levi [88], air is entrained when (i) the operatingspeed exceeds the upper coating speed and (ii) the dynamic contact angle reaches180◦. This would then result in coating failure. Surface roughness of the substratecan also promote air entrainment, whereas the wettability of the substrate has anegligible effect on air entrainment [89]. On the other hand, low surface tension candecrease the extent of air entrainment at constant liquid viscosity for a low-viscosityliquid [90].

28.2.1.2 PrintingPrinting is an alternative technique for slurry processing. Whereas the casting tech-nique has advantages in fabricating large area cathodes and continuous operations,printing is convenient for fabricating cathodes of different shapes and designs.Screen printing and ink-jet printing are the two major categories of printingprocesses.

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28.2.1.2.1 Screen Printing In screen printing, a paste containing active mate-rials, solvents, and additives is applied through a mesh screen onto a substrate.This film is then dried and cured. The process is simple, highly reproducible, andefficient in large-scale production [91]. In addition, no post-annealing process isneeded [11]. Obtaining a homogeneous and stable paste with desirable rheologicalproperties, such as viscosity, is very important. Another key issue is increasing andoptimizing the adhesion strength between the substrate and the printed thick film.Otherwise, the film can delaminate.

Adhesion strength can be improved by introducing a bis-phenol epoxy systemto cathode slurries. It has been reported that a ratio of epoxy and dicyandiamideof 1/0.1 enhances the adhesion between substrates and LiCoO2 films, wheredicyandiamide serves as a curing agent to remove the epoxy ring and complete theadhesion process [92], so that the epoxy resin can be used for the paste vehicle.Terpineol, mineral spirits, and butyl cellosolve comprised the solvent, with emphosPS-21A as the dispersant. The resistance and surface roughness decreased withincreasing amounts of butyl cellosolve, which was due to its ability to decrease theviscosity of LiCoO2 paste. The LiCoO2 film with the addition of epoxy had a highadhesive strength between the film and substrate and no delamination. However,epoxy tended to segregate while curing and increased the surface roughness ofthe film. Electrical shorts can occur between the cathode and anode if the surfaceroughness is too high. Therefore, ethyl cellulose resin was often added to the pasteas a surface roughness controller. A ratio of epoxy/ethyl cellulose of 1/3 was foundto effectively decrease the surface roughness of LiCoO2 films [92]. The dischargecapacity of these LiCoO2 films was low, however, compared to films producedby other techniques. The low discharge capacity can be ascribed to the epoxysegregation blocking the lithium ions and electron transport inside the cathode.Graphite and carbon black, in a ratio of 4/1, were also added to the cathode pasteas a conducting agent. Surface roughness of LiCoO2 films can also be effectivelyreduced by ball milling the LiCoO2 powder and by introducing conducting additivesin ethanol prior to mixing with other constituents. This procedure has been foundto reduce the coagulation between species [93]. The reduction in coagulationdecreases the difference in the particle size of the powder as well as the repulsiveforce between the vehicle and the powders. The pre-dispersing of the conductiveadditive also led to an increase in discharge capacity from 80 to 125 µAh cm−2 fora LiCoO2 cathode at a loading of 4 wt% [92].

28.2.1.2.2 Ink-jet Printing Computer-controlled ink-jet printing is considereda convenient technique for low-cost fabrication of ultrathin films in various fields[94–96]. Recently, it has been used to fabricate a thin-film cathode for a lithium-ionbattery [34, 97, 98]. (A flowchart is shown in Figure 28.3 [34].) An aluminum foilsubstrate is initially cleaned to remove oil and other contaminants from its surfacebefore it is attached to a piece of paper. A hot-roll press is employed to makesolid particles bind to carboxymethyl cellulose (CMC). The final press procedureincreases the packing density of the electrode.

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300 mg nano-LiCoO2

Ultrasonically mixing with 10 deionized water1.5 mL of a 2 mg/mL commercial surfactant

Ultrasonically mixing for 10 min, age for 30 min

Stable suspension

Transfer 15 mL ink to a cartridge

Print ink on an Al

Dry at 80 °C for 3 h

Hot roll press at 125 °C

Pressed at 10 Mpa

Dry at 90 °C for 12 h

Add 15 mg of carbon black, 1 mL of monoeth-anolamine, and 1.5 mg of carboxymethylcellulose sodium (CMC)

Figure 28.3 Flow chart of fabrication of thin-film LiCoO2 cathodes by ink-jet printing.

An ink-jet printer matched with the appropriate software can apply electrodesin shapes that meet specific design requirements. Electrode thickness can beincreased by repeated printing. For ink-jet printing, the key challenge is to preparethe stable colloidal dispersion containing electrochemically active materials as the‘ink’ for subsequent printing [97]. Two methods for mixing the components canbe found in the literature: ball milling [97] and ultrasonic mixing. It is easier toobtain a highly dispersed, uniform suspension through ball milling than throughultrasonic mixing. However, ball milling can be time consuming and may introduceimpurities from breakdown of the ball mill media. Ultrasonic mixing, however,may also require extra additives, including dispersants, binders, and surfactants.In addition, although ball milling helps to decrease the size of large particles, itcaould cause some structural damage to nanoparticles, resulting in a decrease intheir electrochemical activity.

28.2.1.3 Spin CoatingSpin coating has been used to fabricate cathode materials for lithium-ion batteries[99–106]. Spin coaters are easy to operate and relatively economical since they

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require a relatively small amount of space and instrumentation. The liquid solutionto be spin coated is usually prepared by sol-gel methods [103–105]. Generally, it isdifficult to fabricate a film by sol-gel coating that is thicker than 1 µm and that isfree of cracks [105]. However, adding poly(vinylpyrrolidone) (PVP) to the precursorsolution can help to form a uniform sol and effectively prevent crack formation[107]. Shown below are (i) (Figure 28.4) a diagram of a typical spin-coatingprocess and (ii) (Figure 28.5) a flowchart of the synthesis of LiCoO2 on rigidsubstrates [100].

There are various key parameters in the spin-coating process, including theviscosity of the sol, the rotation speed, the number of deposition steps, type of

Depositedprecursor

Substrate

Vacuum chuck

SPIN COATING

Figure 28.4 Schematic of the spin coating process.

Stainless steel or Au-Al2O3

Deposit prepared solutiononto 0.64 cm2 Au-Al2O3

Pre-heat at 100 °C on hot-plate in air for 2 min to

remove methanol

Heat at 525 °C in air for 1 min

Heat cathode in air at 800 °C for 10 minand dry in vacuum oven at 105 °C for 12 h

Stoichiometric amounts of lithium acetateand cobalt acetate in anhydrous methanol

Spin coat:3000 rpmfor 30 s,30 steps

Desiredamount ofelectrode

Figure 28.5 Flowchart of the fabrication of thin-film LiCoO2 cathodes by spin coating.

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substrate, and heat treatment method. The viscosity of the sol can be controlled bychanging the molar weight of PVP. Rotational speed is also important in preventingcrack formation since it is used to regulate the amount of sol on the substrateduring the spin-coating process. This is critical to preventing the formation ofcracks. A crack-free film has also been fabricated by spin coating an LiCoO2 filmon an Au substrate at a rotational speed of 3000 rpm. Spinning at lower rotationalspeeds, however, leads to cracking of coatings.

The choice of substrate also has a significant effect on the electrochemicalperformance of cathode layers. Maranchi et al. [100] compared the effect of stainlesssteel and Au-Al2O3 substrates on an LiCoO2 layer. It was found that stainless steelreacted with lithium and cobalt precursors and formed impurities includingLi3CrO4, CoFe2O4, and CoCr2O4. For an Au-Al2O3 substrate, no impurity wasdetected. An LiCoO2 cathode on stainless steel had a very high first charge capacity(∼325 µAh). However, the irreversible capacity loss during the first cycle was alsovery high (∼64%). The coulombic efficiency gradually increased in subsequentcycles and reached ∼85% by the 10th cycle. The poor coulombic efficiency wasascribed to the reaction between LiCoO2 and the substrate. The first charge anddischarge capacity of LiCoO2 on an Au-Al2O3 substrate was ∼58 and ∼50 µAh,corresponding to a first cycle coulombic efficiency of 86%. The coulombic efficiencywas found to increase to 97% by the fifth cycle.

28.2.2Vacuum Techniques

It is usually difficult to investigate lithium intercalation and deintercalation behaviorwith composite cathodes because of the nonuniform potential distributions andunknown electrode surface area [104]. To avoid this problem, researchers replacedcomposite electrodes with thin-film electrodes, making vacuum techniques a toolof choice in small-scale bench top research. Many techniques have been developedfor fabrication of thin-film electrodes, including chemical vapor deposition (CVD)[108–111], electrostatic spray deposition (ESD) [112–117], pulsed laser deposition(PLD) [2, 118–121], and radio frequency (RF) sputtering. Vacuum systems aretypically required in each of these techniques. Each technique for fabricatingLiCoO2 cathodes will be addressed below.

28.2.2.1 Chemical Vapor DepositionIt has been reported that LiCoO2 with the desired high-temperature crystallinephase can be fabricated by CVD at temperatures as low as 450 ◦C [110]. CVD offersexcellent control of stoichiometry, crystallinity, density, and microstructure [108].Figure 28.6 shows a schematic of the metal organic chemical vapor deposition(MOCVD) process [110]. The liquid injection MOCVD apparatus consists of a CVDreactor with a vacuum system and liquid source delivery system with a microsyringepump and vaporizer. The vaporizer is composed of a stainless steel chamber, astainless steel mesh filter, a diaphragm vacuum gauge, and a heating system.Carrier gas containing precursors, solvents, and oxidants is uniformly supplied

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946 28 Cathode Manufacture for Lithium-Ion Batteries

O2

N2

Micro-SyringePump

MFC

MFCVaporizer

Chamber

Throttle valve

Rotary Pump

RPOUT

Shower head

Substrate

Metering Valve

ON/OFF Valve

Bellows Valve

Pressure Gauge

Heated Line

Heater

Figure 28.6 Schematic of the liquid injection MOCVD apparatus.

onto a substrate through a showerhead-type nozzle. When the single-mixturesources are pumped into the vaporizer, they evaporate and are carried into thereactor by the carrier gas. The typical deposition conditions for a LiCoO2 cathodeare summarized in Table 28.1 [110].

The influence of several parameters, including deposition temperature, the ratioof lithium to cobalt (Li/Co), and annealing temperature, on film morphologyand electrode performance has been investigated [108, 110, 111]. Depositiontemperature affects the crystallinity and morphology of LiCoO2. The crystallizedLiCoO2 films grew with preferred orientation of (003) as the temperature wasincreased from 270 ◦C. The lowest intensity of (003) basal plane was observed at400 ◦C. Also, surface roughness increased with increasing temperature. Figure 28.7shows the morphology of deposited films at 450 ◦C with Li/Co = 0.7. Figure 28.7aand b show the SEM• surface and cross-section image of a deposited thin-filmQ2respectively [110]. As the Li/Co decreased from 0.9 to 0.7, the homogeneity of themorphology increased and surface roughness decreased. The activation energy ofthe deposition rate was found to be 3.41 kcal mol−1, indicating that the deposition

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Table 28.1 Deposition conditions of LiCoO2 cathodes by liquid delivery MOCVD.

Precursors of Li and Co Li(TMHD)a, Co(TMHD)3

Solvent THF (Tetrahydrofuran, C4H8O)Deposition temperature 270–450 ◦CVaporizer temperature 260 ◦CSubstrate Pt/Ti/SiO2/SiSystem pressure 1 TorrPost-annealing temperature 700 ◦C, in O2 for 30 min

aTMHD: 2,2,6,6-tetramethyl-3,5-heptanedionato; C11H19O2.

333 nm

CVD-PtLiCoO2

(a) (b) (c)

Figure 28.7 Morphologies of deposited thin films at 450 ◦Cwith Li/Co = 0.7 (a) SEM surface, (b) SEM cross section,and (c) trench structure.

reaction was probably controlled by gas-phase mass transfer above 300 ◦C. A thinfilm deposited at 450 ◦C with an Li/Co ratio of 0.8 showed a maximum dischargecapacity of 34 µAh cm−2 and capacity retention of 64% after 100 cycles. Thedischarge capacity retention was increased by 18% by annealing the sample at700 ◦C in air for 30 min.

The trench structure has a larger surface area than a planar structure for a givenvolume. CVD can provide good step coverage when applied to a trench structure.Figure 28.7c shows the trench morphology of a CVD-coated LiCoO2/Pt specimen[111]. The thin film covers the trench structure well. The increase in cathode surfacearea improves the discharge capacity of the LiCoO2 cathode. An improvement of130% in the initial discharge capacity of a trench structure compared with thatof a planar structure was achieved with an input Li/Co ratio of 1.2. However, therecharge capability of the film was found to suffer due to the poor conformal growthin the trench structure [108].

28.2.2.2 Electrostatic Spray DepositionESD or electrostatic spray pyrolysis (ESP) has been applied to fabricate metal oxidethin films [122–124]. This technique holds some advantages, including simplesetup and high deposition efficiency [116]. During the ESD process, a precursorsolution is atomized into an aerosol that is directed toward a heated substrateby an electric field to form a thin layer. Several physical and chemical processes

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12

3

4

5

Figure 28.8 Process involved in ESD. 1, spray formation;2, droplet transport, evaporation, disruption; 3, preferentiallanding; 4, discharge, droplet spreading, penetration, drying;and 5, surface diffusion reaction.

occur sequentially or simultaneously during ESD (see Figure 28.8) [116]: sprayformation; droplet transport, evaporation, and disruption; preferential landing ofdroplets; discharge, droplet spreading, penetration of droplet solution, and drying;and surface diffusion reaction.

d ∝ ε1/6r

(Q

k

)1/3

(28.1)

The parameters d, εr,Q , and k are the diameter of the droplets emitted at the jet(the primary droplet size), the relative permittivity of the solution, the feed rate orflow rate of the solution, and the electrical conductivity of the solution, respectively.All of these processes influence the morphology of the deposited layer. A detaileddescription has been reported by Chen et al. [116].

Figure 28.9 shows the vertical ESD setup [115]. The setup operates in a fumehood. The voltage is applied to the nozzle to cause a pressure difference betweenthe top levels of the substrate. Temperature is controlled by a heating element.A rotary pump feeds the precursor solution into the nozzle (a hollow needle orcapillary) and controls the flow rate. A high positive voltage in the solution atthe needle orifice causes the precursor solution to flow through the nozzle, anda positively charged spray is generated. The deposition conditions of the LiCoO2

cathode are summarized in Table 28.2 [115, 116].Several parameters that affect the morphology of LiCoO2 cathodes have been

reported [115]. Pore size increases with increasing flow rate of the precursorsolution, in agreement with Equation 28.1. Substrate temperature is the main factordetermining the cathode morphology. Generally, a higher substrate temperature

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Substrateholder

Heatingelement

Thermocouple

Substrate

Spray

Drain

Nozzle

LayerGround

Power supply

0 to+30 kV

Precursorsolution

−

+

Pump

mV−+

Figure 28.9 Schematic illustration of the vertical ESD setup.

Table 28.2 Deposition conditions of LiCoO2 cathodes by ESD.

Precursors of Li and Co Li(CH3COO)·2H2O, Co(NO3)2·6H2OSolvents 15 vol% ethanol, 85 vol% butyl carbitolSubstrate temperature 230–500 ◦CFlow rate 0.16–8 ml h−1

Substrate Stainless steelVoltage 8–10 kVDistance between nozzle to substrate 2–6 cm

results in a more porous layer, since more solution in the droplets evaporatesbefore arriving at the substrate. The droplets cannot spread well, and manylamellar particles are formed. This increases the effect of preferential landing.A longer deposition time usually also results in a more porous layer since solutiondroplets spread on the previously formed LiCoO2. However, the surface tension ofthe LiCoO2 layer is lower than that of the substrate, which results in poor spreadingand formation of discrete particles. Consequently, the surface roughness of theLiCoO2 layer increases and the agglomeration is more severe.

The electric field strength can affect the morphology of the LiCoO2 cathodesby influencing the flight time of the charged particles [116]. Higher electric fieldstrength leads to a shorter flight time and less solvent evaporation. Thus, thedroplets spread more homogeneously on the substrate surface. A higher electricfield can also decrease or even eliminate the preferential landing effect. Above

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the onset voltage, higher applied voltages lead to more densely formed layers. Thesurface roughness of the ceramic substrate also significantly affects the morphologyof the LiCoO2 layer, since cracks or other defects present in the substrate lead tosevere agglomeration [116]. While the morphology of the LiCoO2 cathodes isnegligibly dependent on the concentration of precursor solution, it depends on theboiling point of solvents. Solvents with higher boiling points mean slow evaporationof solvents, which enhances spreading after the droplets arrive at the substrate[116]. Generally, the lithium ion chemical diffusion coefficients are in the rangebetween 10−13 and 10−12 cm2 s−1 for cathodes prepared in this way [123].

28.2.2.3 Pulsed Laser DepositionPLD is another technique used in the fabrication of thin-film electrodes forlithium-ion batteries [2, 118, 119, 125–129], and this can produce dense, highquality films. However, there are many variable parameters in this process includinglaser power, oxygen pressure, substrate temperature, distance between target andsubstrate, deposition time, and post-annealing or in-situ annealing temperaturesthat define the structure, stoichiometry, and electrochemical performance of theelectrodes [2]. The effect of these variable parameters on the structure, morphology,and electrochemical performance of thin-film electrodes has been reported. Ithas been found that the choice of substrate and the nature of the transparentconducting oxide top layer influence the orientation and crystallinity of the LiCoO2

thin film. For most of the LiCoO2 films, LiCoO2 (003) is the strongest line. Withthe proper substrates, it might be possible to grow non-(003)-textured LiCoO2 films[118], which could have better electrochemical performance because it is likely thatlithium ion diffusion during electrochemical cycling would be faster within the Liplanes than in the perpendicular direction.

Figure 28.10 shows a typical PLD setup [127]. There is a leak valve in the PLDchamber to control operating conditions. Targets are highly dense pellets and aremounted on a target holder inside the chamber. The target is ablated by either a KrF(248 nm) or an ArF (193 nm) excimer laser at a certain frequency. The laser fluencecan be controlled by adjusting the distance between the substrate and the target.Typical operating parameters are summarized in Table 28.3 [118, 119, 127, 129].

The substrate and annealing temperature are very important for the PLD process,since they affect the crystallinity and surface roughness of thin films. Usually, highersubstrate and annealing temperatures lead to higher crystallinity [127, 129] and

Target

Plume

Diff pump

LensGas Inlet

Excimer laser beam

Substrate holderon heater

TargetCarousel

Figure 28.10 Schematic sketch of a PLD system.

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Table 28.3 Typical operating conditions in PLD.

Excimer laser ArF (193 nm), KrF (248 nm)Frequency 5–10 HzDistance between substrates and targets 5–8.5 cmBeam intensity 0.64–14 J cm−2

Substrate temperature 300–700 ◦COxygen partial pressure 50–3000 mTorr

lower surface roughness of thin films. Higher substrate temperature also increasedthe reversible capacities of a LiNi0.5 Mn1.5 O4 film, which is due to less polarizationof the cell at elevated temperatures [129]. However, higher annealing temperatureslead to lower discharge capacity. This decreased from 166.2 to 8.9 mAh g−1 whenthe annealing temperature was increased from 500 to 700 ◦C for LiNi0.8 Co0.2 O2 [2].The severe capacity drop in a sample that was post-annealed at a higher temperaturemay have been due to deterioration in the layered structure. Additionally, theannealing time also has a significant effect on the extent of crystallization anddegree of preferential orientation of the LiCoO2 films [119]. A short annealingtime under a high annealing temperature limits deterioration of the initially strongpreferential orientation of the polycrystalline film. In contrast, a prolonged exposureto high temperatures causes an outgrowth of crystals.

Oxygen partial pressure is another important factor. Impurity, such as Co3O4

for LiCoO2, and Mn2O3 for LiMn2O4, formed at low oxygen partial pressure (e.g.,50 m Torr). The impurity decreases or disappears at high oxygen partial pressures(e.g., 300 m Torr) [118, 129]. Usually, low oxygen partial pressure leads to densethin films and poorly defined grains. In contrast, high oxygen partial pressure leadsto big and well-defined grains as well as high porosity. The better crystallizationfrom higher oxygen partial pressure is ascribed to the lower deposition rate [129].Therefore, it is essential to process under a suitable oxygen partial pressure in PLDprocess. It has been reported that LiNi0.5Mn1.5O4 films deposited at 600 ◦C and anoxygen partial pressure of 200 m Torr demonstrated the highest electrochemicalactivity, the largest initial capacity, and the best capacity retention [129]. Its reversiblecapacity (120 mAh g−1) by PLD technique was lower than that by ESD technique(140 mAh g−1). However, its discharge capacity retention was higher, 96 and 91%after 50 cycles for PLD and ESD, respectively [129, 130].

28.2.2.4 Radio Frequency (RF) SputteringVarious important factors influence deposited cathodes in RF sputtering, includingsubstrate temperature, annealing temperature, type of substrate, film thickness,and RF power. (Typical operating parameters are summarized in Table 28.4[119, 131–138].) Usually, post-annealing is not necessary for amorphous thinfilms. However, it is required for fabrication of highly crystallized thin films. Thedeposition and annealing temperature effect on an LiCoO2 thin film has beenreported by Liao et al. [135]. Films deposited at 250 ◦C and then annealed at 600 ◦C

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952 28 Cathode Manufacture for Lithium-Ion Batteries

Table 28.4 Typical operation conditions in RF-sputtering.

Background pressure 7–20 mTorrAr/O2 3/1Ar and O2 total flow rate 12–20 sccmRF power 50–210 WSubstrate temperature 100–600 ◦CTarget to substrate distance 0.2–8 cm

exhibited superior discharge capacity to those deposited at ambient temperatureand then annealed at 600 ◦C or those deposited at 600 ◦C without annealing.The film deposited at 600 ◦C showed submicron grains and needle-like grains,whereas the films deposited at ambient temperature and 250 ◦C showed nano-sizegrains. This was ascribed to an effect similar to annealing of higher substratetemperature which facilitated grain growth. Higher substrate temperature alsoimproved the crystallinity of LiCoO2 [133]. However, higher substrate temperaturealso increased void fraction, which reduced the contact area between the electrolyteand cathode as well as the contact area between the grains. Consequently, thecell resistance increased [131]. Therefore, an appropriate substrate temperaturedepends on a compromise of the crystallinity of active material and the conductivityof the cathode. In addition, the type of substrate affects the surface roughness ofdeposited film.

Film thickness is another important factor that affects grain orientation. Bates andco-workers have reported that a LiCoO2 film developed different texture accordingto the film thickness to minimize either the volume strain energy developed duringannealing or the surface energy [131]. The grains in this texture were preferentiallyoriented with (101) and (104) planes parallel to the substrate for films thicker than1 µm. In contrast, they were oriented with (003) plane parallel to the substrate forfilms thinner than 0.5 µm. The crossover thickness was between 0.1 and 0.2 µm,where the percentages of grains with a (003) plane are 100 and 40%, respectively.The grain orientations relative to the direction of lithium diffusion are shown inFigure 28.11 [131]. Lithium ions transported primarily through grains for films with

(003) (101) (104)O

Li Co

Figure 28.11 Illustration of the preferred orientation of theLiCoO2 grains versus the direction of current flow.

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28.3 Summary 953

highly (101)- to (104)-oriented grains and primarily through the grain boundariesfor those with highly (003)-oriented grains [131].

RF power affects particle size of deposited film, and higher RF power leads tolarger particle size. For example, the particle size of LiCoO2 increases from 40 to150 nm when the RF power is increased from 80 to 200 W. Higher RF power alsoleads to higher discharge capacity and better capacity retention [136].

28.2.3Other Processing – Molten Carbonate Method

The molten carbonate process is not widely adopted for the fabrication of LiCoO2

film, and information about this process is limited. To date, it has only been reportedby Uchida et al. [139, 140]. A preferentially (003)-oriented LiCoO2 thin-film wasobtained by oxidation of a thin cobalt film in molten Li + K carbonate (62 : 38 mol%)onto a gold substrate at 923 K under an atmosphere of O2 and CO2 in a ratio of 9 to1. The thickness of the LiCoO2 film depends on the oxidation period. The diffusioncoefficient of lithium ions has been determined to be ∼10−12 cm2 s−1.

28.3Summary

Various processes for fabrication of lithium ion battery cathodes are discussedin this chapter. All processes except the molten carbonate method havebeen widely applied in research and production. Table 28.5 summarizesthe performance of LiCoO2 electrodes fabricated by each of these processes.The electrochemical performance is highly dependent on the processingconditions.

Excellent results have been achieved with each method, as shown in Table 28.5.However, each process has its advantages and disadvantages. In general, tapecasting, slot-die coating, screen printing, ink-jet printing, and spin coating arefor fabrication of composite electrodes. CVD, ESD, PLD, RF-sputtering, andink-jet printing are more suitable for fabrication of ultrathin electrodes becausethey are better for controlling the thickness of thin films. In addition, sincethe thin films are very dense and usually have high packing density, they aresuitable for thin-film batteries. However, CVD, ESD, PLD, and RF-sputteringrequire expensive equipment, and the processes are complicated. Additionally,these processes require post-annealing at high temperature, which may causesome unwanted substrate–film reactions, cracking, or peeling due to thermaleffects. It is also more difficult to control the stoichiometry of thin films in theseprocesses.

Stoichiometry is relatively easy to control with spin coating, screen printing, andink-jet printing, and these methods are less expensive. They are also more suited topreparing large-scale electrodes. The requirement of a suspension system in spin

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954 28 Cathode Manufacture for Lithium-Ion Batteries

Table 28.5 Major electrochemical performance of LiCoO2 cathodes from different processes.

Processes Batteries components Major performance

Screen coating LiCoO2/1 M LiPF6 inEC-DEC (1/1 vol)/Li [92]

Initial discharge capacity of 125 µAh/cm2

when cycled between 3.0 and 4.2 V; with4 wt% graphite and carbon black pre-ballmilling in ethanol for 24 h before mixing withthe pastes, curing at 100 ◦C for 1 h.

Ink-jet printing LiCoO2/1 M LiPF6 inEC-DMC (1/1 vol)/Li [34]

Initial discharge capacity of 125 mAh/g with95% capacity maintained after 100 cycleswhen cycled between 3.0 and 4.2 V at192 µA/cm2, 1.2 µm thick.

Spin coating LiCoO2/1 M LiPF6 inEC-DEC (2/1 vol)/Li [100]

Initial discharge capacity of 78 µAh/cm2aandcoulombic efficiency increasing from 86 to97% in five cycles when cycled between 3.1and 4.2 V at 31.25 µA/cm2; annealed in air at800 ◦C for 10 min.

CVD LiCoO2/1 M LiClO4 inPC/Li [110]

Maximum discharge capacity of34 µAh/cm2 µm and capacity retention of 64%after cycling 100 times when cycled between4.3 and 3.3 V at 100 µA/cm2; deposited at 450◦C with Li/Co = 0.8, annealed at 700 ◦C for30 min in an oxygen ambient.

ESD LiCoO2/1 M LiPF6 inEC-DEC (1/1 vol)/Li [113]

Specific discharge capacity of 130 mAh/gwhen cycled between 2.1 and 4.3 V at100 µA/cm2; containing 15% nano-SiO2,annealed at 700 ◦C for 2 h.

PLD LiCoO2/1 M LiClO4 inPPC/Li [118]

Initial discharge capacity of 118 mAh/g with0.5% degradation per cycle when cycledbetween 3.5 and 4.4 V at 5 µA/cm2; fabricatedat Ts = 700 ◦C, PO2 = 2000 mTorr.

RF-sputtering LiCoO2/1 M LiPF6 inEC-DMC (1/1 vol)/Li [136]

Initial discharge capacity of 61 µAh/cm2 µmand capacity retention of 88% after 25 cycleswhen cycled between 4.2 and 3.0 V at20 µA/cm2; deposited at 55 ◦C with a workingpressure of 0.5 Pa and a RF power of 200 W.

PC, propylene carbonate; EC, ethylene carbonate; DEC, diethyl carbonate; PPC, propylene carbonate;DMC, dimethyl carbonate;anormalized by substrate area (0.64 cm2).

coating, screen printing, and ink-jet printing makes it convenient for electrodemodification, such as adding conductive material to improve the electrical con-ductivity of the electrodes. However, the complicated suspension systems containa number of organic additives, and these processes are thus less environmen-tally friendly. In addition, the packing density of electrodes fabricated from theseprocesses is relatively low.

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‘‘keywords/abstract

Dear Author,

Keywords and abstracts will not be included in the print version of your chapter butonly in the online version. Please check and/or supply keywords. If you suppliedan abstract with the manuscript, please check the typeset version. If you did notprovide an abstract, the section headings will be displayed instead of an abstracttext in the online version.

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Abstract

Keywords

slurry processing; casting; slot-die coating; printing; spin coating; chemical vapordeposition; pulsed laser deposition; RF and laser sputtering; molten carbonatemethod

Affiliation

Affiliation for the authors: Jianlin Li1, Claus Daniel1,2, and David L. Wood III1

1Oak Ridge National Laboratory, Materials Science and Technology Division, OakRidge, TN 37831-6083, USA2University of Tennessee, Department of Materials Science and Engineering,Knoxville, TN 37996, USA

Daniel c28.tex V1 - 04/05/2011 7:29pm Page 958

Queries in Chapter 28

Q1. AUTHOR: The word ‘‘Processing’’ has been changed to ‘‘Manufacture’’ Isthis OK?

Q2. Please confirm if this abbreviation ‘SEM’ needs to be spelt out. If yes, pleaseprovide the expansion.

Q3. Please provide the page range for Reference 12.

Q4. Please clarify if this article has since been published. If so, please provide theyear of publication for Reference 50.

Q5. Please provide the author’s forename for Reference 67.

Q6. Please provide the book title for References 78, 80.

Q7. Please provide the patent number for References 82 and 83.