Cathode material for a lithium-ion rechargeable battery

Abstract

A positive electrode for a rechargeable battery, comprising a lithium metal oxide powder having a layered crystal structure and having the formula Li.sub.xTm.sub.yHm.sub.zO.sub.6, with 3x4.8, 0.60y2.0, 0.60z2.0, and x+y+z=6, wherein Tm is one or more transition metals of the group consisting of Mn, Fe, Co, Ni, and Cr; wherein Hm is one or more metals of the group consisting of Zr, Nb, Mo and W. The lithium metal oxide powder may comprise dopants and have the formula Li.sub.xTm.sub.yHm.sub.zM.sub.mO.sub.6 A, wherein A is either one or more elements of the group consisting of F, S or N; and M is either one or more metal of the group consisting of Ca, Sr, Y, La, Ce and Zr, with either >0 or m>0, 0.05, m0.05 and x+y+z+m=6.

Claims

1. A positive electrode for a rechargeable battery, comprising a lithium metal oxide powder having a layered crystal structure and having the formula Li.sub.xTm.sub.yHm.sub.zO.sub.6, with 3x4.8, 0.60y2.0, 0.60z2.0, and x+y+z=6, wherein Tm is one or more transition metals selected from the group consisting of Mn, Fe, Co, Ni, and Cr; wherein Hm is one or more metals selected from the group consisting of Zr, Nb, Mo and W, and wherein the lithium metal oxide powder has a diffraction peak intensity ratio R between the largest peak at 18.51.5 and the largest peak at 43.51.5 in the X-ray powder diffractometry using a Cu-K line as the X-ray source, with R=I.sub.1/I.sub.2, where I.sub.1 is the integrated intensity of the largest peak at 18.51.5 and I.sub.2 is the integrated intensity of the largest peak at 43.51.5, wherein R>1.0, wherein the lithium metal oxide powder comprises dopants, and has the formula Li.sub.xTm.sub.yHm.sub.zM.sub.mO.sub.6-A.sub., wherein A is either one or more elements selected from the group consisting of F, S or N; and M is either one or more metals selected from the group consisting of Ca, Sr, Y, La, Ce and Zr, with either >0 or m >0, 0.05, m0.05 and x+y+z+m=6.

2. The positive electrode of claim 1, wherein x3 and Hm=Nb.

3. The positive electrode of claim 1, wherein x=4 and Hm is either W or Mo, and Tm is either Cr or Mn.

4. The positive electrode of claim 1, wherein x=4, Hm=W and Tm is either Mn or Ni.sub.nMn.sub.mCo.sub.c, with 0n1, 0m1, 0c1, and n+m+c=1.

5. The positive electrode of claim 1, wherein x=4, Tm=Ni, Hm=W, and the structure is C2/m.

6. A rechargeable battery comprising a positive electrode, the positive electrode comprising a lithium metal oxide powder having a layered crystal structure and having the formula Li.sub.xTm.sub.xHm.sub.zO.sub.6, with 3x4.8, 0.60y2.0, 0.60z2.0, and x+y+z=6, wherein Tm is one or more transition metals selected from the group consisting of Mn, Fe, Co, Ni, and Cr; wherein Hm is one or more metals selected from the group consisting of Zr, Nb, Mo and W, and wherein the lithium metal oxide powder has a diffraction peak intensity ratio R between the largest peak at 18.51.5 and the largest peak at 43.51.5 in the X-ray powder diffractometry using a Cu-K line as the X-ray source, with R=I.sub.1/I.sub.2, where I.sub.1 is the integrated intensity of the largest peak at 18.51.5 and I.sub.2 is the integrated intensity of the largest peak at 43.51.5, wherein R>1.0, wherein the lithium metal oxide powder of the positive electrode comprises dopants, and has the formula Li.sub.xTm.sub.yHm.sub.zMO.sub.6-A.sub., wherein A is either one or more elements selected from the group consisting of F, S or N; and M is either one or more metals selected from the group consisting of Ca, Sr, Y, La, Ce and Zr, with either >0 or m >0, 0.05, m0.05 and x+y+z+m=6.

7. The rechargeable battery of claim 6, wherein x3 and Hm=Nb.

8. The rechargeable battery of claim 6, wherein x=4 and Hm is either W or Mo, and Tm is either Cr or Mn.

9. A rechargeable battery comprising a positive electrode, the positive electrode comprising a lithium metal oxide powder having a layered crystal structure and having the formula Li.sub.xTm.sub.yHm.sub.zO.sub.6, with 3x4.8, 0.60y2.0, 0.60z2.0, and x+y+z=6, wherein Tm is one or more transition metals selected from the group consisting of Mn, Fe, Co, Ni, and Cr; wherein Hm is one or more metals selected from the group consisting of Zr, Nb, Mo and W, and wherein the lithium metal oxide powder has a diffraction peak intensity ratio R between the largest peak at 18.51.5 and the largest peak at 43.51.5 in the X-ray powder diffractometry using a Cu-K line as the X-ray source, with R=I.sub.1/I.sub.2, where I.sub.1 is the integrated intensity of the largest peak at 18.51.5 and I.sub.2 is the integrated intensity of the largest peak at 43.51.5, wherein R>1.0, wherein x3 and Hm=Nb.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: X-ray powder diffraction (XRD) pattern of the as prepared Li.sub.4NiWO.sub.6 cathode material

(2) FIG. 2: Charge/Discharge curves of Li.sub.4NiWO.sub.6 between 3.0 and 4.1V

(3) FIG. 3: Cycling performance of Li.sub.4NiWO.sub.6 between 3.0 and 4.1V

(4) FIG. 4: Ex-situ XRD pattern of Li.sub.4NiWO.sub.6 between 3.0 and 4.1V

(5) FIG. 5: Ex-situ XRD pattern of Li.sub.4NiWO.sub.6 between 1.5 and 4.9V

(6) FIG. 6: Ex-situ XRD pattern of Li.sub.3Ni.sub.2NbO.sub.6 cathode materials

(7) FIG. 7: XRD pattern of layered cathode material (a) Li.sub.4MnWO.sub.6, (b) Li.sub.4Ni.sub.0.6Mn.sub.0.2Co.sub.0.2WO.sub.6 and (c) Li.sub.4CrMoO.sub.6.

DETAILED DESCRIPTION

(8) This invention focuses on the discovery of novel layered materials, which can be used as cathode material in the application of a lithium ion battery. Considering the benefits of high amounts of available Li ion per formula, the group of layered materials, like Li.sub.4MMO.sub.6 is investigated, where M refers to transition metals such as Ni and Mn. In this invention, so-called heavy metals, like W, Zr, Nb or Mo are introduced as the component M. These heavy metals possess a high valence stateup to +6and are likely to stabilize Li-rich layered structures, like in the compounds Li.sub.4WO.sub.5, Li.sub.4MoO.sub.5 and Li.sub.3NbO.sub.4. When applied as cathode material in a battery, a stable crystalline structure is a necessary requirement to obtain good cyclability. It is believed that the addition of these heavy metals will also stabilize the layered structure of Li.sub.4MMO.sub.6. Some of the described lithium metal oxide powders are known from the prior art, but were never developed for use in a lithium rechargeable battery. For example, Mandal in Chem. Mater. 2005; 17, 2310-2316 describes Li.sub.4MWO.sub.6 perovskites; Mather in Journal of Solid State Chemistry 124, 214-219 (1996) describes Li.sub.3Ni.sub.2NbO.sub.6 rock-salt structures; Vega-Glez in Revista Mexicana de Fisica 51 (3) 299-303 describes rock salt Li.sub.(3-3x)Co.sub.4xNb.sub.(1-x)O.sub.4 structures;

(9) The materials according to the invention have the general formula Li.sub.xTm.sub.yHm.sub.zO.sub.6 (Tm is transition metal and Hm is heavy metal), wherein x=3-4.8, y=0.60-2.0, z=0.60-2.0, x+y+z=6, where small deviations in the values of x, y and z are possible however when additional impurities or dopants are present; Tm being one or more transition metals Mn, Fe, Co, Ni, Cr, Ti and V; and Hm being one or more heavy metals Zr, Nb, Mo, W and Ru. There might be some dopants in the structure, resulting in the formula Li.sub.xTm.sub.yHm.sub.zO.sub.6-A.sub., with A being either one or more of F, S or N. The materials can also contain metallic dopants and have the general formula Li.sub.xTm.sub.yHm.sub.zM.sub.mO.sub.6-A.sub., where M is one or more of Ca, Sr, Y, La, Ce and Zr, and x+y+z+m=6. This group of materials contains more than one available lithium ion for deintercalation when applied in a battery. In some embodiments, the amount of available lithium ions reaches up to 4, and the redox reaction of the transition metals, like Ni.sup.2+ oxidizing to Ni.sup.4+, or Cr.sup.2+ oxidizing to Cr.sup.6+ makes the reversible release and uptake of four lithium ions possible, which is promising for achieving a high capacity.

(10) The materials according to the invention all have a layered structure. The distribution of atoms within the layers leads to a structure of lithium layers alternating with Li/Tm/Hm layers. In each layer, all the cations are octahedrally surrounded by oxygen. Specifically, if the crystal structure is r-3M, Li and Tm atoms are statistically distributed in the same octahedral site, surrounding octahedrals of HmO.sub.6. If the crystal structure is a superstructure of r-3M then Li/Tm/Hm might show cation ordering within the metal slabs. The ordering of the cations into a well layered structure is a key factor related to the electrochemical performance, such as cyclability, as a highly ordered structure is required to obtain a good cycling performance. The ordering of a layered structure can be evaluated by investigating the Bragg peak ratios in the X-ray diffraction pattern, specifically the ratio of the integrated intensities of the peaks at resp. 18.51.5 and 43.51.5, each of these being the largest in that region. In order to get an ordered structure, with low cation mixing, the ratio of the Bragg peaks should be greater than 0.55, preferably 0.7 or even 0.9. In some embodiments, the peak ratio is 1.5 or more, 1.7 or more, even 2.0 or more. The practical upper limit for the ratio is somewhere around 2.5.

(11) This invention observes that the material according to the invention has a relatively stable layered structure when applied in a battery. The layered structure basically remains during cycling, which is a similar behavior than for the commercial cathode materials LCO and NMC, and is believed to be an important factor for the cycling stability in batteries. In one embodiment, the composition of Li.sub.4NiWO.sub.6 keeps the layered structure with a space group of C2/m during the 1.sup.st cycle of charge/discharge in a potential range of 2.7-4.3 V. It is only at higher voltages like 4.9 V or lower voltages like 1.5 V that the layered structure starts to collapse. It is also observed that the ratio of the Bragg peaks at 18.51.5 ((001) plane) and 43.51.5 ((131) plane) changes during charge. When charging up to a high voltage, the peak ratio decreases. So the ordering of structure is lowered during charge and the structure has the risk of collapsing. Even worse, if the pristine material had a certain amount of cation mixing in the layered structure, upon charging, the structure would collapse even at low voltage. Therefore, this again proves that the ordering of the layered structure has an important effect on the electrochemical performance of material in batteries. A highly ordered material is preferred in the application of batteries with good cyclability.

(12) Coin Cell Test

(13) The layered lithium-rich transition metal oxide powders are electrochemically tested at a small scale in a coin cell, as follows: the pristine powder is mixed with carbon at a ratio 4:1 (active material: carbon) and ball milled together for 12 hours. The active mixture is further blended with a binder material to a composition of 72:10:18 (active material: binder: carbon), and is loaded on an aluminum foil. The negative electrode is a lithium foil having a thickness of 500 m (origin: Hosen). The electrode's active loading is 2.5 mg/cm.sup.2. The separator (from SK Innovation) is located between the positive electrode and a negative electrode. 1M LiPF.sub.6 in EC/DMC (1:2) is used as electrolyte, and dropped between separator and electrodes. The as-prepared coin cells are charged/discharged in a potential range of 3.0-4.1 V for 40 cycles. The current density is 14.5 mA/g (corresponding to C/20, where 1C represents a full charge or discharge in one hour). This invention observes a good cyclability of coin cells when the layered lithium metal oxide according to the invention is used as positive electrode. In one embodiment, the coin cell test of Li.sub.4NiWO.sub.6 shows that the discharge capacity is almost constant after 40 cycles in the potential range of 3-4.IV.

(14) Ex-Situ XRD Coin Cell Test

(15) The layered lithium-rich transition metal oxide powders according to the invention are ex-situ tested through X-ray diffraction after been electrochemically charged at a small scale in a coin cell. The coin cell are made as described above. The prepared cells are electrochemically tested as shown in Table 1, at a current density of 14.5 mA/g. Then the coin cell is disassembled and the cathode electrode is tested by X-ray diffraction.

(16) TABLE-US-00001 TABLE 1 Ex-situ XRD schedule Test No Charge voltage (V) Discharge voltage (V) 1 4.1 2 4.3 3 4.9 4 4.9 3.5 5 4.9 2.7 6 4.9 1.5
X-Ray Diffraction Test

(17) The cathode material are tested by X-ray diffraction to check the structural properties. The XRD tests are conducted in a Ultima IV device (Rigaku corp.) and the X-ray source is Cu-K. This invention provides cathode materials having a layered structure like the commercial cathode materials LCO and NMC. In the case of LCO and NMC, they possess a space group of R-3m and their ordering of layer structure can be evaluated by the ratio of the integrated intensities of Bragg peaks (003) to (104) in the XRD pattern. Similar to LCO and NMC, the material according to the invention can also be evaluated by such a peak ratio to check the ordering of the layered structure. In the measured patterns of this invention, Bragg peaks located at 28 equal to 18.51.5 and 43.51.5 are chosen, each being the largest in the region. The ratio of the integrated intensities of these two peaks can be calculated and gives an indication of the ordering degree of the layered structure. A high peak ratio means that the layered structure is highly ordered, where low peak ratios indicate a poor ordering in the layered structure.

(18) The invention is further illustrated in the following examples:

Example 1: Preparation and Electrochemical Properties of Li.SUB.4.NiWO.SUB.6

(19) This example presents the layered cathode material Li.sub.4NiWO.sub.6. This material is prepared following the procedure below:

(20) 1. Blending of precursors: 1.25% excess lithium hydroxide monohydrate (LiOHH.sub.2O), with WO.sub.3 and nickel acetate (Ni(CH.sub.3COO).sub.2-4H.sub.2O) powders in just proportions are homogeneously blended in just proportions to obtain the stoichiometric composition.

(21) 2. Sintering: after mixing, the mixture is sintered at 1000 C. for 12 hours under dry air. Dry air is continuously pumped into the sintering equipment at a flow of 5 L/min.

(22) 3. Post-treatment: after sintering, the sintered material is crushed and sieved so as to obtain a non-agglomerated powder.

(23) The obtained powder is labelled E1, and investigated by X-ray diffraction.

(24) FIG. 1 shows the obtained XRD pattern (2Th=2), together with the fitting curve of Rietveld refinement by TOPAS 3.0 software. A single phase with a C2/m space group is fitting in the measured pattern. Refinement gives a layered structure, with Li layers alternating with Li/Ni/W layers. Bragg peak (001) at 18.5 and Bragg peak (131) at 43.7 are chosen to evaluate the ordering of structure. The ratio of these Bragg peaks is around 1.8, its value is given in Table 2 below. As described in the X-ray diffraction test, a big ratio is an indication of high ordering of the layered structure. Thus, the E1 sample has a highly ordered layered structure.

(25) The electrochemical performance of E1 is tested in a coin cell as described in Coin cell test. FIG. 2 (Voltage in V versus capacity in mAh/g) shows the first cycle curve of the coin cell based on E1the charge is the continuous line, the discharge is the dotted line. A relatively low polarization is observed. The charge and discharge curve are roughly parallel indicating that no major structural changes happened during the cycle. The discharge capacity is around 90 mAh/g. FIG. 3 (discharge capacity in mAh/g versus cycle number N) presents the cycling performance of the coin cell. It is observed that the discharge capacity is almost constant over 40 cycles. This indicates a good cyclability of the battery when E1 is used as cathode material, which is related to the highly ordered layered structure of E1. Therefore, this example shows that the layered cathode material according to this invention and having the formula Li.sub.4NiWO.sub.6 has a good cycling stability. Even though the specific capacity per weight is not high enough compared to e.g. LCO, considering the high weight of tungsten in the composition, the specific capacity per volume will be considerable.

Example 2: Crystal Structure of Li.SUB.4.NiWO.SUB.6 .During Charge and Discharge

(26) This example investigates the stability of the crystal structure of sample E1 during a charge/discharge cycle. Ex-situ XRD tests of E1 are processed following the description in Ex-situ XRD test. FIG. 4 shows ex-situ XRD patterns of the 1st cycle between 3.0 and 4.1V. Pattern (a) refers to E1 after being soaked in the electrolyte, which means that the E1 cathode is assembled in the coin cell and then disassembled without any electrochemical treatment like charging/discharging.

(27) Pattern (b) is corresponding to the E1 sample after being charged up to 4.1V in the coin cell. Pattern (c) represents the XRD pattern of the E1 sample extracted from the coin cell after one cycle of charge/discharge in the range of 3.0-4.1 V. It can be seen that these patterns are quite similar to each other and thus, during the 1.sup.st cycle, the layered structure of E1 remains unchanged.

(28) FIG. 5 shows the ex-situ XRD patterns in a 1st cycle between 1.5 and 4.9V. Pattern (a) refers to the soaked E1 sample, while patterns (b) to (g) refer to the E1 sample extracted from the coin cell at different cutoff voltages during charge/discharge. Patterns (b) to (d) are charged to 4.1V, 4.3 V and 4.9 V respectively, corresponding to Test No 1-3 in Table 1. Pattern (e) to (g) are first charged to 4.9 V and then discharged to 3.5 V, 2.7 V and 1.5 V respectively, corresponding to Test No 4-6 in Table 1. Comparing patterns (a) to (f), there is basically no change, except for slight changes in pattern (d), which corresponds to the sample charged to 4.9 V. Thus until charging to 4.9 V, the layered structure remains intact. During discharge, the structure keeps a layered characteristic until 1.5 V. At 1.5 V, (pattern (g)) we observe peak broadening thus the layered structure starts to collapse. The consistence of layered structure is an indication of good cycle stability, which has been observed in the commercial cathode materials like LCO and NMC. As the E1 sample presents a good consistence of layered structure, this provides support to its high cycling stability.

(29) From pattern (a) to pattern (c), the layer structure is retained, but it is clearly observed that the intensity of Bragg peak at 18.50 decreases and the intensity of Bragg peak at 43.70 increases. This leads to the intensity ratio R of the Bragg peak at 18.51.5 to the peak at 43.51.5 decreasing from (a) to (c). Thus, the ordering of layered structure is gradually weakening during charging. This can be simply explained since more and more lithium is exacted upon charging, there should be more and more vacancies leading to possibilities of cation mixing, which undermines the stability of the layered structure. With further charging, like up to 4.9 V, the layered structure starts to collapse due to over-delithiation.

Example 3: Preparation and Structural Properties of Li.SUB.3.Ni.SUB.2.NbO.SUB.6

(30) This example presents the layered cathode material Li.sub.3Ni.sub.2NbO.sub.6. This material is prepared following the procedure below:

(31) 1. Blending of precursors: 2.5% excess lithium hydroxide monohydrate (LiOH.H.sub.2O), Nb.sub.2O.sub.5 and nickel acetate (Ni(CH.sub.3COO).sub.2.4H.sub.2O) powder are homogenously blended in just proportions to obtain the stoichiometric composition.

(32) 2. Sintering: after mixing, the mixture is sintered at 1000 C. for 12 hours under dry air. Dry air is continuously pumped into the sintering equipment at a flow of 5 L/min.

(33) 3. Post-treatment: after sintering, the sintered material is crushed and sieved so as to obtain a non-agglomerated powder. The obtained powder is labelled E2.

(34) By changing the sintering conditions, two other samples are obtained, labelled E3 and E4. E3 refers to a sample sintered at 1000 C. for 24 hours, while E4 refers to a sample sintered at 1100 C. for 12 hours. E2, E3 and E4 are tested following the procedure in X-ray diffraction test. FIG. 6 shows the obtained XRD patterns, where (a), (b) and (c) correspond to resp. samples E2, E3 and E4. All the patterns are fitting into a single phase with space group Fddd, having a layered structure like sample E1. The ordering of structure is evaluated by choosing the Bragg peaks at 19.0 ((111) plane) and 43.2 ((206) plane). The peaks ratios R of E2, E3 and E4 are all smaller than 0.8 (see Table 2), which indicates that there are large amounts of cation mixing. The poor ordering of layered structure generally cannot lead to a good electrochemical performance. However, it can be seen from the patterns that the peak ratio is improving from (a) to (c), thus, by changing the temperature and other conditions, it is feasible to improve the degree of ordering for Li.sub.3Ni.sub.2NbO.sub.6 material. As discussed in Example 1, a highly ordered layered structure can be indicative of a good electrochemical performance. In the composition of Li.sub.3Ni.sub.2NbO.sub.6, the stoichiometric number of Ni is two. Since each Ni.sup.2*/Ni.sup.4+ redox reaction can allow two Li-ions participating in the delithiation/lithiation, in the compound of Li.sub.3Ni.sub.2NbO.sub.6, all the three Li-ions can be (de)intercalated. Thus, this material potentially possesses a high capacity. The electrochemical tests of E2, E3 and E4 show that these phases are electrochemically active, and the discharge capacity of the first cycle is around 40 mAh/g when cycled in the range of 1.5-4.9 V. If the layered character can be improved further, excellent electrochemical properties are feasible as discussed above.

Example 4: Preparation of Other Layered Materials

(35) A layered lithium metal oxide powder Li.sub.4MnWO.sub.6 is prepared following the same procedure as described in Example 1, except that the Ni source is replaced by a Mn source being MnO.sub.2. The obtained powder is labelled E5. Similar to E5, a layered powder Li.sub.4Ni.sub.0.6Mn.sub.0.2Co.sub.0.2WO.sub.6 is prepared in the same procedure, except that the Mn source is replaced by Ni.sub.0.6Mn.sub.0.2Co.sub.0.2OOH. This powder is labelled E6. A third material Li.sub.4CrMoO.sub.6 is also prepared by the same method as E5, the precursors being changed to LiOH.H.sub.2O, Cr.sub.2O.sub.3 and MoO.sub.3. The obtained powder is labelled E7.

(36) FIG. 7 shows the XRD patterns of E5, E6 and E7, which correspond to patterns (a), (b) and (c), respectively. These patterns are all fitted into single phases with a layered structure. The ratio R of peaks located at 18.51.5 and 43.51.5 is given in Table 2, and are very high. These large peak ratios indicate that the E5, E6 and E7 samples have a highly ordered layered structure. The samples E3 and E6 have a similar composition than sample E1.

(37) In E5, the Mn ion has the same valence state as Ni in E1, which is supposed to play main role in the electrochemical activity. Thus, E5 can have a similar electrochemical behavior as E1, which had a high cycling stability in the coin cell test. For E6, it is equivalent to E1 but with partially substituting Ni for Mn and Co to achieve the transition metal ratio 3:1:1 (Ni:Mn:Co). It has been observed that the substitution of Ni by Mn and Co can stabilize the structure and provide good cyclability. Thus, E6 potentially possesses a good stability as cathode material in the application of a Li ion battery.

(38) In the E7 sample, both Cr and Mo have various valence states, which could raise up to +6, thus this material can be highly electrochemical active. Generally, the Cr ion has a larger possibility to play a main role in the electrochemical behavior, in contrast to the Mo ion. During the delithiation/lithiation, the redox couple of Cr.sup.2+/Cr.sup.6+ can allow all the Li-ions in the formula to participate, which can lead to a high capacity in the Li ion battery. Therefore, sample E7 has a high potential as cathode material in the battery application.

(39) TABLE-US-00002 TABLE 2 overview of ratio of Bragg peaks Integr. area Integr. area Simplified of peak at of peak at Sample ID Composition 18.5 1.5 43.5 1.5 Ratio R E1 LiNiW 411.2 231.3 1.78 E2 LiNiNb 50.2 471.3 0.11 E3 LiNiNb 103.5 453.8 0.23 E4 LiNiNb 268.2 475.2 0.56 E5 LiMnW 290.0 187.8 1.54 E6 Li-NMC622-W 525.7 256.8 2.05 E7 LiCrMo 304.2 146 2.08

(40) The lithium metal oxides according to the invention have a high crystallographic densitythat is the unit cell mass divided by the unit cell volume, based on Topas refinement calculationsas is shown in Table 3. Such high values of crystallographic density will allow to achieve high values of volumetric capacity in a battery.

(41) TABLE-US-00003 TABLE 3 overview of crystal density by TOPAS refinement Compositions LiNiW LiMnW LiCrMo Li-NMC-W LiNiNb Sample ID E1 E5 E7 E6 E2 Density 5.65 6.401 4.103 5.695 5.715 (g/cm.sup.3)