Design of high energy density MCMB/Li[Ni1/3Mn1/3Co1/3]O2 cells
for PHEV purposes Honghe Zheng1,*, Gao Liu*, Xiangyun Song, Paul Ridgway and Vince Battaglia*, z Lawrence Berkeley National Laboratory, 1 Cyclotron Rd, Berkeley, CA 94720, USA
Introduction Energy density is one of the important criteria for lithium-ion batteries to meet the aggressive requirements for PHEV applications. According to the recently announced PHEV goals by the USABC, a system energy density of 207 Wh/L is required (with an assumption that only 70% is available for all electric driving) to meet the 40-mile, all-electric-driving target. Reducing inactive material content and increasing electrode thickness are important ways to increase the energy density of a lithium-ion battery. We have reported the energy density improvement of the Li[Ni1/3Mn1/3Co1/3]O2 (L333) cathode
using minimum amounts of inactive materials[1]. That study investigated the effects of electrode thickness on the electrochemical behavior of graphite anodes and Li[Ni1/3Mn1/3Co1/3]O2-cathodes. In this presentation we
show that on the electrode scale combining the optimized MCMB anode and Li[Ni1/3Mn1/3Co1/3]O2 cathode surpasses the PHEV 40-mile energy density goal by 50%.
Experiment MCMB was supplied by Osaka Gas, Japan and Li[Ni1/3Mn1/3Co1/3]O2 was supplied by Seimi, USA. A slurry consisting of different amounts of active material, PVdF, and acetlylene black was prepared by mixing in 1-methyl-2-pyrrolidone (1MP). Coated films on copper foil for MCMB and on aluminum foil for Li[Ni1/3Mn1/3Co1/3]O2
were prepared by the motorized doctor blade method. All
of the films with different active material loadings were compressed to 35% porosity using a calendering machine. Coin cells were assembled in an argon-filled glove box. The separator employed was Celgard 2400. 1M LiPF6/EC+DEC(1:2) was used as the electrolyte. Electrochemical measurements were performed by using a Maccor battery cycler.
Results and discussion
Fig.1 shows the effect of electrode thickness on the rate performance for both the MCMB-based anode and the Li[Ni1/3Mn1/3Co1/3]O2-based cathode. From this figure,
it is seen that rate performances of the anode and the cathode as a function of the electrode thickness are quite different. The capacity of at which the anode hits the rate
1 On leave from Henan Normal University, P.R.China
* Electrochemical active member z E-mail: VSBattaglia@lbl.gov
mass transfer limit varies dramatically with thicknees and C-rate, where as the capacity of the cathode shows a steady decline as a function of rate before hitting a mass transfer limit and is mass transfer limit is less dependent on C-rate.
Fig.2 Variations of turning point capacity for electrodes of different graphites and L333 obtained from rate capability curves similar to those of Fig.1. Fig.2 was obtained by plotting the capacity versus current density of an electrode corresponding to the point just before the bend in the curve of the rate-capability curves of Figure 1. (The performances of three graphites and L333 are displayed.) This figure indicates that. for discharge rates below ca. 3 C, the rate performance of the three graphite anodes is worse than that of the Li[Ni1/3Mn1/3Co1/3]O2 cathode. In other words, the anode limits the rate performance of the cell for discharges longer than 20 minutes. The data also suggest that cells with discharge rates greater than 3C can not be made with L333 cathodes. For urban driving, 20 mph is considered the average driving speed. Therefore, the 40-mile battery system should be optimized for a 2 hr discharge, i.e. C/2 rate. Based on the data of figure 2, the cycleable capacity of the cell should not exceed 4 mAh/cm2.
Fig.3 Power cycling of MCMB/Li[Ni1/3Mn1/3Co1/3]O2 full
cells. Cathode contains a: 8% PVdF; b: 2% PVdF.
Fig. 3 shows the power cycling of two
MCMB/Li[Ni1/3Mn1/3Co1/3]O2 coin cells we designed for PHEV purposes. These cells are cycled with a P/4 Charge to 4.3V, and a P/2 Discharge to 70% depth of discharge (DOD), with a 1-hour constant voltage hold at the top of charge. The two cells contain cathodes with different binder contents, 2% and 8%. The cell with the cathode that contains 2% binder has an initial useable energy density of 350 Wh/l (volume includes the working area from Al to Cu current collector). The cell with the cathode that contains 8% binder has an initial useable energy density of 310 Wh/l. The electrode -based energy density of the both systems exceeds the PHEV system requirements with excellent cycling behavior. Meeting the system requirement will require additional engineering effort. The cells are still cycling in our laboratory. Reference 1. Honghe Zheng, Gao Liu, Vince Battaglia et. al, ECS Trans. 11:1-7. 2008