Chromatography: Analysis of Phosphate and Manganese degradation Products in Aged lithium Ion...

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Rosanne Slingsby, Kate Comstock, and Paul Voelker March 18, 2015

Analysis of Phosphate and Manganese Degradation Products in Aged Lithium Ion Batteries

Part #: PP71583-EN 0315S

2

Li-ion Battery Analysis: IC-HRMS What Steps Are Involved?

IC-HRMS Thermo Scientific™ Q Exactive™ Orbitrap™ MS

• Component Identification in Untargeted and Unknown Workflows

IC-CD

Time (min) 125 135 145 155 165 175 185 m/z

0

100

169.0272

C 4 H 10 O 5 P

155.0115 C 3 H 8 O 5 P

125.0009 C 2 H 6 O 4 P

139.0166

C 3 H 8 O 4 P

Phosphate esters

Chemical formula

Exact mass

Delta ppm

C2H6O4P 125.0009 -0.1

C3H8O4P 139.0166 0.2

C3H8O5P 155.0115 0.1

C4H10O5P 169.0272 0.4

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1.  IC Separation using a KOH eluent

2.  Full scan MS/MS acquisition

3.  Component ID based on HRAM Data

4.  Propose Structure

Source for Dimethyl phosphate image: CSID:2982799, http://www.chemspider.com/Chemical-Structure.2982799.html (accessed 00:59, Feb 5, 2015)

3

Ion Chromatography Coupled to High Resolution Mass Spectrometry

Eluent Generator (OH– or H+)

Conductivity Detector

High-Pressure

Non-Metallic Pump

H2O

Autosampler Electrolytic

Eluent Suppressor

CR-TC

Separation column

Pump

Solvent/H2O

CD Thermo Scientific

Q ExactiveTM

HRMS

C-trap HCD Cell Segmented Quadrupole

RF Lens

Injection flatapole

Electrospray inlet

4

Methods

•  IC Parameters Column: Thermo Scientific™ Dionex™ IonPac™AG11, AS11 (2 mm) Eluent: 1mM KOH from 0 to 5 minutes, 1-30 mM KOH from 5 to 25 minutes 30-65 mM KOH from 25.1-45 minutes Eluent Source: Thermo Scientific Dionex EGC 500 KOH Cartridge Flow Rate: 0.25 mL/min Inj. Volume: 2.5 µL Temperature: 30 ˚C Detection: Suppressed Conductivity, Thermo Scientific™ Dionex™ AERS™ 500 (2 mm) Suppressor AutoSuppression, recycle mode

Post column solvent: 90/10 Acetonitrile/water, 0.25 mL/min

•  MS Parameters HRAM full scan MS and data dependent top 3 MS/MS were collected at resolution 70K and 17.5K, respectively Stepped NCE setting were: 30, 40, 60.

5

7. Methylsulfonate 8. Pyruvate 9. Chlorite 10. Valerate 11. Monochloroacetate 12. Bromate 13. Chloride 14. Nitrite 15. Trifluoroacetate 16. Bromide 17. Nitrate 18. Chlorate 19. Selenite 20. Carbonate 21. Malonate 22. Maleate 23. Sulfate 24. Oxalate 25. Ketomalonate 26. Tungstate 27. Phthalate 28. Phosphate 29. Chromate 30. Citrate 31. Tricarballylate 32. Isocitrate 33. cis-Aconitate 34. trans-Aconitate

Peaks: 1. Isopropylmethylphosphonate

mg/L 2. Quinate 3. Fluoride 4. Acetate 5. Propionate 6. Formate

0

10

µS

0 5 15 Minutes 10

1 2

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Monovalent Divalent Trivalent

Anion Exchange Gradients: Dionex IonPac AS11 Separation of Anions

6

Lithium Ion Battery (LiB) Samples

•  Overall Objectives •  Screen samples to identify changes among sample types •  Use ion exchange separation to help identify analyte properties •  Identify as many components as possible

•  Samples •  Control •  Calendar aged 20% loss in capacity •  Cycle Aged 20% loss in capacity •  Additional Cycle Aged 45% loss in capacity

•  Other Injections •  DI water blank •  Process control blank

7

Preparation of LiB Anode Samples

• Anodes were cut to known weight • Samples were sonicated and rinsed in deionized water • Extracts were filtered thru Whatman PP 0.45 µm filters • Weight losses were calculated • Filtered extracts were injected into the IC-CD-HRMS

system

8

IC-CD Chromatograms of Anode Samples

e:\lib\nov20-run\va-3-pp 11/20/14 21:49:03AS11 2mm 250ul/minRT: 0.00 - 55.00

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

µS

3.77

4.0715.924.91

5.27 17.9215.569.78 10.73 27.71 49.1524.688.15 14.94 26.675.81 23.01 54.8250.66 53.58

NL:1.19E1ECD_1 UV MA-0-PP

RT: 0.00 - 54.99

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

µS

4.91 16.1415.8922.94

14.2117.925.22 27.79

24.10 49.1448.5710.73 26.66 41.6613.867.00 9.76 50.65 51.53 53.1919.66 28.64

NL:1.54E1ECD_1 UV UA-1-PP

RT: 0.00 - 54.99

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

µS

4.91

16.1415.87

22.95

14.2027.77

17.925.17

49.7249.0226.6724.1313.86 50.67

NL:3.21E1ECD_1 UV va-3-pp

Control Calendar Aged 20% Loss Cycle Aged 45% Loss

Sulfate 17.12

Phosphate

Monovalent Divalent Trivalent components

9

IC-HRMS Chromatograms of Anode Samples


2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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20

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5.32

9.82

8.214.11 16.2211.07

15.593.93 27.7424.7514.06

NL:3.09E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS MA-0-PP

RT: 0.00 - 54.99

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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5

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15

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23.02

4.16 5.31 16.1914.237.04 8.163.76 9.81 15.576.22 27.77

24.13 41.7217.9911.07 24.30 49.7513.99

NL:2.57E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS UA-1-PP

RT: 0.09 - 55.00

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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5

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15

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23.00

14.24

5.294.20 16.19

27.7315.553.59 27.868.153.32 9.80

7.01 49.7926.7317.98 24.16 49.1913.95 41.7910.63 53.27

NL:2.79E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS va-3-pp

Monovalent Divalent Trivalent components

Control Calendar Aged 20% Loss Cycle Aged 45% Loss

10

Anionic Compounds and Classes Found in LiB Samples to Date

• Solvents- Methyl carbonate

•  Inorganic Anions- sulfate, phosphate, hexafluorophosphate etc

• Carboxylic acids- succinate, malate, malonate, oxalate etc

• Organic sulfonates – propylsulfonate

• Sulfate esters

• Phosphate esters

• Fluorophosphate esters

11

Example Data Analysis - Identify Methyl Carbonate

E:\LiB\Nov20-Run\VA-3-PP 11/20/14 21:49:03AS11 2mm 250ul/minRT: 0.04 - 55.00

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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23.00

14.245.294.20 16.19

27.7315.553.59 27.868.153.32 9.807.01 49.7926.7317.98 24.16 49.1913.95 41.7910.63 53.2728.2118.86 47.442.23 37.581.26 38.48 50.6136.4529.7822.53 31.87 46.0833.04 42.33

NL :2.79E 9B as e P eak F : F TMS -‐ p E S I F ull ms [50.00-‐750.00] MS VA -‐3-‐P P

VA-3-PP #1865 RT: 4.21 AV: 1 NL: 1.41E8T: FTMS - p ESI Full ms [50.00-750.00]

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210m/z

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75.0087C2 H3 O 3

122.9853C2 H4 O 4 P89.0245

C3 H5 O 360.9930C H O 3

59.0137C2 H3 O 2

RT: 0.00 - 55.00

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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4.20

17.11

NL : 1.75E 8m/z= 74.38-‐75.38 F : F TMS -‐ p E S I F ull ms [50.00-‐750.00] MS VA -‐3-‐P P

VA-3-PP #1854 RT: 4.19 AV: 1 NL: 2.21E7F: FTMS - p ESI d Full ms2 [email protected] [50.00-100.00]

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210m/z

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75.0088C2 H3 O 3

Full Scan c-gram Peak at 4.20 minutes EIC of 75.0088 m/z Delta 0.4 ppm MS2 at 4.20 min.

C2H3O3

12

E:\LiB\Nov20-Run\VA-3-PP 11/20/14 21:49:03AS11 2mm 250ul/minRT: 0.09 - 55.00

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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23.00

14.24

5.29 4.20 16.19

27.7315.553.59 27.868.153.32 9.803.24 7.01 49.7926.7317.98 24.16 49.1913.95 41.7910.63 53.2718.31 18.48 28.21 47.442.23 37.581.26 38.48 50.6136.4529.78 31.87 44.9633.04 42.33

NL:2.79E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS VA-3-PP

VA-3-PP #1568-1694 RT: 3.58-3.84 AV: 32 NL: 5.89E7T: FTMS - p ESI Full ms [50.00-750.00]

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240m/z

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169.0272C4 H10 O 5 P

139.0166C3 H8 O 4 P

125.0009C2 H6 O 4 P

155.0115C3 H8 O 5 P

185.0222C11 H5 O 360.9930

C H O 3153.0323

C4 H10 O 4 P119.0349C4 H7 O 4

133.0507C5 H9 O 4

89.0245C3 H5 O 3

179.0562C6 H11 O 6

110.9853C H4 O 4 P

163.0613C6 H11 O 5

103.0401C4 H7 O 3

RT: 0.00 - 55.00 SM: 7B

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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5.30

3.87

5.63

NL:1.70E8m/z= 138.51-139.51 F: FTMS - p ESI Full ms [50.00-750.00] MS VA-3-PP

Early Eluting Phosphate Esters

Phosphate esters

Chemical formula

Exact mass Delta ppm

C2H6O4P 125.0009 -0.1

C3H8O4P 139.0166 0.2

C3H8O5P 155.0115 0.1

C4H10O5P 169.0272 0.4

(RT 3.6-3.8 minutes)

EIC of 139.01 m/z

RT 3.6-3.8 minutes

Base peak chromatogram

13

Later Eluting Phosphate Esters


0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

0

50

1000

50

1000

50

10017.16

23.0014.245.294.20 16.19 27.733.59 8.15 9.80 49.7926.7317.9813.95 41.79 53.2714.24

3.65 17.065.94 23.03 28.94 30.9226.152.78 38.5335.459.80 52.9046.5313.78 41.0721.93 45.378.68 49.8019.24 33.70 41.9914.39

24.333.36 27.0114.85 22.993.74 17.2310.01 47.1938.53 54.2640.0922.1211.97 49.420.86 36.8635.3130.26 43.50 45.56 50.9733.578.256.96

NL: 2.79E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS va-3-pp

NL: 3.23E7Base Peak m/z= 282.49-283.49 F: FTMS - p ESI Full ms [50.00-750.00] MS va-3-pp

NL: 2.70E7Base Peak m/z= 212.51-213.51 F: FTMS - p ESI Full ms [50.00-750.00] MS va-3-pp

va-3-pp #6257-6338 RT: 14.19-14.36 AV: 21 SB: 129 14.50-15.08 , 13.35-13.92 NL: 1.22E8T: FTMS - p ESI Full ms [50.00-750.00]

60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300m/z

0

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140.9958C2 H6 O5 P

125.0009C2 H6 O4 P

110.9852C H4 O4 P78.9590

O3 P

282.9991C4 H13 O10 P2267.0039

C4 H13 O9 P2

121.0295C7 H5 O2

213.0170C5 H10 O7 P

236.9935C3 H11 O8 P2

96.9600H O4 S

(RT14.2-14.4 minutes)

14

Analysis of an Unknown- Ethanetricarboxylate


2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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23.00

14.24

5.294.20 16.19

27.733.598.15

3.32 9.807.01 49.7926.7317.98 24.16 49.1913.95 41.799.97 53.27



60 70 80 90 100 110 120 130 140 150 160 170 180 190 200m/z

0

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117.0193C4 H5 O4

103.0037C3 H3 O4

161.0092C5 H5 O6

59.0137C2 H3 O2 118.9986

C3 H3 O5133.0143C4 H5 O5

73.0295C3 H5 O2

60.9929C H O3

178.9317H2 O6 F P2

149.0092C4 H5 O6

99.0088C4 H3 O3

173.0092C6 H5 O6

115.0037C4 H3 O4

Delta 0.2 ppm

Trivalent elution region

C5H5O6

15

Simple Case - Propylsulfonate


2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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23.00

14.24

5.294.20 16.19

27.733.598.15

3.32 9.807.01 49.7926.7317.98 24.16 49.1913.95 41.799.97 53.27



60 70 80 90 100 110 120 130 140 150 160 170 180 190 200m/z

0

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123.0121C3 H7 O3 S

79.9572O3 S

16

Chemical Formula for Propylsulfonate Help from HRMS Data

Chemical formulae, Mass 123.01 Chemical formulae, Mass 123.0121 Formula Delta, ppm Formula Delta, ppm

1 C6H3O3 10.0 1 C3H7O3S -0.3 2 C3H7O3S -17.4 2 C6H3O3 27.1

17

Summary: ESI(-) Mode Peaks from Sample VA

RT: 0.44 - 55.00

5 10 15 20 25 30 35 40 45 50 55Time (min)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

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5.294.20

16.19

27.733.59

27.86

8.15

3.32 9.80

7.01 49.7926.73

17.9824.16 49.19

13.95 41.7953.2718.21

18.66 47.4428.792.23 47.1537.58 50.6136.4529.78 41.34


6.21

14.24

15.55

17.22

23.03

Retention time Masses Delta (ppm) Possible ID

3.3-3.8 several Phosphate esters

4.20 75.0088 0.4 CH3O3 Methyl carbonate

6.21 112.9810 0.6 CH3O3FP Methylfluorophosphate

8.15 123.0121 -0.3 C3H7O3S Propylsulfonate

14.24 several Phosphate esters

15.55 117.0193 0.3 C4H5O4 Succinate

16.19 103.0036 -0.2 C3H3O4 Malonate

15.62 133.0137 0.4 C4H5O5 Malate

17.22 98.9601 0 HSO4

23.03 98.9696 -0.2 H2PO4

27.73 161.0092 0.2 C5H5O6

41.79 176.9360 0.3 H3P2O7

49.19 175.0249 0.5 C6H7O6

18

Summary

•  Ion chromatography provides ion exchange separations of anionic (or cationic) sample components

• The IC with a conductivity detector is coupled to HRMS to provide information in the elucidation of unknowns

• Analytes are eluted in the order of monovalent<divalent<trivalent<higher by ion exchange separation so information is provided on key structural features

• To date we have found components from the aging of LiB anodes in several chemical classes including carboxylic acids, esters, phosphate esters, fluorophosphate esters, sulfate esters, as well as inorganic anions

19

Lithium Ion Battery Anode Samples Analysis

•  Anode samples •  Control Cell Shelf Aged. •  Calendar Aged. Exhibited 20% loss in capacity. •  Cycle Aged. Exhibited 20% loss in capacity. •  Additional Cycle Aged. Exhibited 45% loss in capacity.

•  Objective •  To identify the impurity and degradant present in the sample group. •  To correlate the analysis results with the batteries performance.

•  IC-HRMS Analysis and software •  Thermo Scientific Dionex IC combined with the Q Exactive HRMS was used

for separation and identification. •  Thermo Scientific™ SIEVE™ software used for component extraction and

differential analysis. The Chem Spider report with the high resolution data base for known component screening. Thermo Scientific™ Mass Frontier™ was used for structural elucidation.

20

Comprehensive Li-ion Battery Analysis Workflow : IC-HRMS

HR MS Analysis Full Scan-MS/MS

Ion Separation

Components Identified .

_________________ . _________________ . _________________ . _________________ . _________________ . _________________

Component ID (Chem Spider and high resolution ion database)

Sample Preparation

Thermo Scientific high resolution accurate mass ion database contains accurate masses for common anions and elemental compositions. Users can quickly identify the common anions by database search.

Report

Thermo Scientific Dionex ICS-2100 System

Q Exactive MS SIEVE Software

Component Extraction Differential Analysis

High Resolution Anion Database . __________ .__________ . __________ .__________ . __________ .__________

21

Schematic of Q Exactive Benchtop LC-MS/MS

22

Q Exactive MS Specifications •  Max resolution: 140,000 at m/z 200

•  Scan speed: up to 12 HZ (at 17.5K)

•  Mass Accuracy •  < 3 ppm external

•  < 1 ppm internal

•  Mass range for full scans: 50 < m/z < 6000

•  Intra-scan dynamic range: > 5000:1

•  Sensitivity •  Full MS: 500 fg Buspirone on column S/N 100:1

•  SIM: 50 fg Buspirone on column S/N 100:1

•  Polarity Switching •  One full cycle in < 1 sec (one full scan positive mode and one full scan

negative mode at resolution setting of 35,000)

Resolution at m/z 200

Max. Scan Speed (Hz)

17.500 12 35.000 7 70.000 3

140.000 1.5

23

Why Use Q Exactive HRMS?

• Q Exactive High Resolution Accurate Mass (HRAM) data provides ultimate confidence for qualitative and quantitative analysis.

• High sensitivity, rapid polarity switching ensure detection of structurally diverse compounds at all level.

• The HRAM full scan and MS/MS provide rich information for component identification and structure elucidation

• Coupled with SIEVE and other Thermo Scientific software, QExactive MS is best suited for known and unknown impurity and degradant analysis for Li-ion battery and other industrial applications.

24

Q Exactive Instrument Method

• MS Method •  ESI negative ion mode •  AGC target 1e6 •  Full scan MS and data dependent top 3 MS/MS at resolution 70K

and 17.5K •  Stepped NCE: 30, 45, 60 •  Scan range: 50 to 750 m/z

25

HR-MS for Lithium Ion Battery Anode Analysis

• HR-MS unambiguously identifies ion species based on HRAM data

•  Unit mass vs. high resolution accurate mass

m/z (-‐) Unit mass

m/z (-‐) HRAM

Formula (-‐) Ionic Species

97 96.9601 HSO4 Hydrogen Sulfate

97 96.9696 H2PO4 DiHydrogen Phosphate

139 139.0166 C3H8O4P Phosphate Ester

139 139.0071 C3H7O4S Sulfate Ester

26

90 100 110 120 130 140 150 160 170 180 190 m/z 0 10 20 30 40 50 60 70 80 90 100

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139.0166

133.0507 110.9853

120 130 140 150 160 170 180 m/z 0 10 20 30 40 50 60 70 80 90 100

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139.0071

141.0029 UA-1-PP # 1634 RT: 3.73 T:

50 60 70 80 90 100 110 120 130 140 150 160 m/z 0 10 20 30 40 50 60 70 80 90 100

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78.9591 O 3 P

0.8 ppm 110.9853 C H 4 O 4 P

0.5 ppm

139.0166 C 3 H 8 O 4 P

0.5 ppm 62.9642 O 2 P

0.3 ppm

UA-1-PP # 2322 RT: 5.26 AV: 1 NL: 2.84E7 T:

50 60 70 80 90 100 110 120 130 140 150 160 m/z 0 10 20 30 40 50 60 70 80 90 100

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139.0072 C 3 H 7 O 4 S

1.0 ppm 79.9575

O 3 S 1.3 ppm

81.9532 64.9702 H O 2 S

-1.4873 ppm 120.9965 C 3 H 5 O 3 S

-0.1060 ppm

HRAM MS/MS Fragments for Structure Elucidation

(M-H)- (M-H)-

C3H7O4S m/z (-) 139.0071 0.3 ppm

(-) C3H8O4P m/z (-) 139.0166 0.4 ppm

MS/MS

MS/MS

S

O

O

OOHOH P

O

O

O

•  HRAM MS/MS fragments for confident structure characterization

27

HRAM MS/MS Fragments for Structure Elucidation

The structures of co-eluting peaks were identified by MS/MS fragments

OP

O

O

O

OP

O

O

O

OH OP

O

O

O

OH OP

O

O

O

OHOH

ua-1-pp # 1521 RT: 3.48 AV: 1 NL: 5.71E7 T: FTMS - p ESI Full ms [50.00-750.00]

80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 m/z

0 10 20 30 40 50 60 70 80 90

100

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169.0272

155.0116

185.0222 125.0009

139.0166 183.0122 96.9601 112.9856 121.0295

163.0613 200.9865 89.0245 79.9574 190.9916 172.9915

133.0507 149.0456 255.2331 217.0256 101.0608 237.0148 283.2644 274.9611 293.0074

ua-1-pp # 1510 RT: 3.46 AV: 1 NL: 2.72E6 T: FTMS - p ESI d Full ms2 [email protected] [50.00-150.00]

60 80 100 120 140 m/z 0

10 20 30 40 50 60 70 80 90

100

Rel

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125.0010

62.9641 78.9591

111.9568 94.9905


60 80 100 120 140 160 180 m/z 0

10 20 30 40 50 60 70 80 90

100

Rel

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78.9591 110.9853

155.0117 122.9854


60 80 100 120 140 160 180 m/z 0

10 20 30 40 50 60 70 80 90

100 R

elat

ive

Abu

ndan

ce

78.9591

140.9960 169.0273

125.0010


50 100 150 200 m/z 0

10 20 30 40 50 60 70 80 90

100

Rel

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78.9591

122.9854

185.0223 140.9960

28

IC-HRMS Result for Aged Anode

F:\Li-Battary-Paul\Nov20-Run\VA-3-PP 11/20/14 21:49:03AS11 2mm 250ul/min

RT: 0.0 - 55.0 SM: 5G

0 5 10 15 20 25 30 35 40 45 50 55Time (min)

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40

50

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5

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4.0

17.1

4.9 16.1 22.914.2 27.817.95.2 49.748.626.724.113.9 50.717.2

23.014.25.34.2 16.2 27.73.6 27.88.1 9.83.3 49.87.0 26.718.0 24.2 49.213.9 41.810.6 53.3

NL:3.21E1ECD_1 UV VA-3-PP


IC Chromatogram

MS Base Peak Chromatogram

Cycle Aged Sample 45% Loss

29

IC Chromatograms for All Samples

f:\li-battary-paul\nov20-run\ma-0-pp 11/20/14 23:59:15AS11 2mm 250ul/min

RT: 0.0 - 30.0 SM: 7G

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time (min)

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10

20

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20

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10

20

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0

10

20

µS

0

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20

µS

0

10

20

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17.1

3.8 4.1 15.94.9

3.917.1

4.9 16.1 22.9

3.9

17.1

4.9 15.9

17.1

4.9 16.1 22.914.2 27.8

NL:2.50E1ECD_1 UV blk_141120225409

NL:2.50E1ECD_1 UV pc-2-pp

NL:2.50E1ECD_1 UV ma-0-pp

NL:2.50E1ECD_1 UV ua-1-pp

NL:2.50E1ECD_1 UV xa-2-pp

NL:2.50E1ECD_1 UV VA-3-PP

Solvent Blank

Control Cell shelf aged

Calendar-aged 20% loss in capacity

Cycle aged 20% loss in capacity

Process Control


The IC chromatograms show the differences between samples

30

HRMS Base Peak Chromatograph

f:\li-battary-paul\...\blk_141120225409 11/20/14 22:54:09AS11 2mm 250ul/min

RT: 0.0 - 55.0 SM: 5G

0 5 10 15 20 25 30 35 40 45 50 55Time (min)

0

50

1000

50

1000

50

1000

50

1000

50

1000

50

100

5.3 9.88.24.1 16.211.1 15.63.9 27.824.717.2

23.04.2 5.3 16.214.27.0 8.23.8 9.8 27.824.1 41.711.1 49.8

17.2

23.014.24.2 5.3 16.23.5 27.88.2 9.8 49.826.77.1 13.9

23.014.25.34.2 16.2 27.73.6 8.1 9.8 49.87.0 26.718.013.9 41.8

NL: 2.60E9Base Peak m/z= 50.0000-6000.0000 F: FTMS - p ESI Full ms [50.00-750.00] - m/z= 144.9640-144.9654 MS blk_141120225409

NL: 2.60E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS pc-2-pp

NL: 2.60E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS ma-0-pp

NL: 2.60E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS ua-1-pp

NL: 2.60E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS xa-2-pp

NL: 2.60E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS VA-3-PP

Solvent Blank

Control cell shelf aged



Process Control


See zoomed-in view in next slide (Full Scan Negative mode)

31


RT: 0.2 - 54.5 SM: 5G

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54Time (min)

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8.24.1 16.211.1

15.63.9 27.824.713.812.9 18.33.6 26.7

23.0

4.2 5.3 16.214.27.0 8.24.0 9.83.5 6.2 15.6 27.8

24.1 41.711.1 24.3 49.814.0 18.1 49.228.1

23.014.24.2 5.3 16.24.03.5 27.815.68.2 9.8

49.826.77.1 13.913.2 24.2 49.218.2

14.2

5.34.216.2

27.73.6 15.5 27.88.19.83.3

49.87.0 26.718.0 24.2 49.213.9 41.813.4 53.318.6

NL:2.60E8Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS ma-0-pp

NL:2.60E8Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS ua-1-pp

NL:2.60E8Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS xa-2-pp


Yellow –new or increasing

MS Base Peak Chromatograph

Blue – Decrease or disappearing

Control cell shelf aged




MS show different profiles and more peaks Zoomed-in View

32

SIEVE Base Peak Alignments (MS Data)

0-30 min

Zoom In View

40-55 min

33

SIEVE - Trend Intensities and XIC

Trend Intensities RT =11 min

XIC RT =11 min

Component m/z 124.9912 at RT 11.0 min with Elemental Formula C2H5O4S, Ethyl sulfate. The Shelf aged control has high intensity.

34

SIEVE PCA Showing Differences Between Sample Groups

Trend Intensities at RT =11 min m/z 124.9912

PCA plot for all six samples

35

Control Cell Shelf Aged

E:\GM-Li Battery\Nov20-Run\MA-0-PP 11/20/14 23:59:15AS11 2mm 250ul/min

RT: 0.0 - 55.0 SM: 5G

0 5 10 15 20 25 30 35 40 45 50 55Time (min)

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

Rel

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9.8

8.2

4.1 16.211.1

15.63.9 27.824.713.8

NL:2.95E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS MA-0-PP

HRMS Base Peak Chromatogram

1

2

3

4

5

6

7

8

9

10

11 12

13

36

Component Identified from “Control Cell Shelf Aged”

Components idenPfied in Control Sample Peak # RT (min) m/z Formula (-‐) Delta ppm Name* (Based on MS results)**

1 3.9 89.0244 105.0193 119.0350

C3H5O3 C3H5O4 C4H7O4

0.3 -‐0.4 -‐0.3

lactate

2 4.1 75.0087 C2H3O3 -‐0.4 Methyl carbonate 3 5.3 139.0070 C3H7O4S 0 Propyl sulfate 4 8.2 123.0121 C3H7O3S -‐0.1 Propyl sulfonate 5 9.8 140.9864 C2H5O5S 0.3 2-‐hydroxyethyl sulfate 6 11.1 124.9914 C2H5O4S -‐0.3 Ethyl sulfate 7 15.6 117.0193 C4H5O4 0.2 methyl malonate 8 15.7 133.0143 C4H5O5 0.2 3-‐carboxy-‐3-‐hydroxypropanoate 9 16.2 103.0037 C3H3O4 0 2-‐carboxyacetate 10 17.2 96.9601 HO4S -‐0.2 hydrogen sulfate 11 24.7 218.9639 C3H7O7S2 0.2 2-‐hydroxy-‐3-‐sulfopropane-‐1-‐sulfonate 12 26.7 175.0249 C6H7O6 0.3 13 27.8 117.0193 C4H5O4 0.1 2-‐carboxy-‐propanoate

* The compounds are proposed based on database search using HRAM data . The other possible structures are not show. ** The MS data were acquired in ESI negaPve ion mode. The ions reported there are all HRAM single charged negaPve ions. The names listed here are corresponding to the single charge ionic species. *** The notes here apply to other samples in this experiment.

37

Calendar Aged 20% Capacity Loss

E:\GM-Li Battery\Nov20-Run\UA-1-PP 11/21/14 02:09:29AS11 2mm 250ul/min

RT: 1.9 - 50.9 SM: 5G

5 10 15 20 25 30 35 40 45 50Time (min)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

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23.0

4.2 5.3

16.2

14.27.0

8.2

3.8 9.86.2 15.6

27.8

24.1

NL:2.53E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS UA-1-PP


1

2, 3 8

4 5

6

7

9

10

11

12, 13, 14

19

23

20

22

18

21

15,16, 17

24 25 29

26

28

27 30

31

38

Component Identified from Calendar Aged Sample 45% Capacity Loss

Components IdenPfied in Calendar Aged Sample Peak # RT (min) m/z Formula (-‐) Delta ppm Name (Based on MS results)*

1 3.4 To 3.6

125.0009 155.0116 169.0272 185.0222

C2H6O4P C3H8O5P C4H10O5P C4H10O6P

0 0.6 0.6 0.6

Phosphate Esters

2 3.7 139.0166 C3H8O4P 0.5 Phosphoric acid 3 3.9 153.0323 C4H10O4P 0.5 Phosphate 4 4.2 75.0088 C2H3O3 -‐0.2 Methyl Carbonate 5 5.3 139.0071 C3H7O4S 0.4 Propyl sulfate 6 6.2 112.9810 CH3O3FP 0.3 Methyl Phosphorofluoridate 7 7.0 126.9966 C2H5O3FP 0.1 Ethyl phosphorofluoridate 8 8.2 123.0122 C3H7O3S 0.3 Propyl sulfonate 9 9.8 140.9864 C2H5O5S 0.3 2-‐hydroxyethyl sulfate 10 10.7 110.9757 CH3O4S -‐0.3 methyl sulfate 11 11.1 124.9914 C2H5O4S 0.1 Ethyl sulfate 12 14.2 140.9958 C2H6O5P 0.1 2-‐hydroxyethyl hydrogen phosphate

13 14.3 125.0009 C2H6O4P -‐0.1 ethyl hydrogen phosphate 14 14.4 110.9853 CH4O4P -‐0.2 methyl hydrogenphosphate 15 15.3 131.0350 C5H7O4 0 3-‐carboxy-‐2-‐methylpropanoate

16 15.6 117.0193 C4H5O4 0.2 Methyl Malonate 17 15.7 133.0143 C4H5O5 0.2 3-‐carboxy-‐3-‐hydroxypropanoate

18 15.9 117.0194 C4H5O4 0.2 Succinate 19 16.2 103.0037 C3H3O4 0.3 2-‐carboxyacetate 20 16.6 98.9653 HO3FP 0.2 hydrogen phosphorofluoridate 21 17.2 96.9601 HO4S -‐0.2 hydrogen sulfate 22 23.0 96.9696 H2O4P -‐0.5 dihydrogen phosphate 23 24.1 204.9674 C2H7O7P2 0.7 hydrogen (1-‐hydroxy-‐1-‐phosphono-‐ethyl)-‐phosphonate

24 24.3 190.9517 CH5O7P2 1.1 Methyl trihydrogen diphosphate 25 26.7 175.0249 C6H7O6 0.3 Ascorbate 26 27.8 161.0092 C5H5O6 0.1 Ethanetricarboxylate 27 27.9 103.0037 C3H3O4 0.3 28 28.1 133.0143 C4H5O5 0.4 29 41.7 176.9361 H3O7P2 0.9 Trihydrogen diphosphate 30 49.2 175.0249 C6H7O6 0.6 Tricarballylate 31 49.8 204.9990 C6H5O8 0.1


Blue –Decrease or disappearing

39

Cycle Aged Sample 20% Capacity Loss

F:\Li-Battary-Paul\Nov20-Run\XA-2-PP 11/20/14 19:38:48AS11 2mm 250ul/min

RT: 0.0 - 55.0 SM: 5G

0 5 10 15 20 25 30 35 40 45 50 55Time (min)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

Rel

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23.014.2

4.2

5.3 16.2

4.0

3.5

27.815.6

8.2

9.8

49.826.77.1

13.913.4 24.2 49.218.211.9 24.4

NL:1.96E9Base Peak F: FTMS - p ESI Full ms [50.00-750.00] MS XA-2-PP


1

2

4

5

6

8 9

3

19

26 14

18

21

24

30

31 29 10

11, 12, 13

15, 16, 17

20 7

23 25

28

22

32 27

40

Component Identified from Cycle Aged 20% Loss in Capacity Components IdenPfied in Cycle Aged Sample

Peak # RT (min) m/z Formula (-‐) Delta ppm Name (Based on MS results)* 1 3.2-‐3.6 125.0009

155.0116 169.0272 185.0222


0 0.6 0.6 0.6

Phosphate Esters

2 3.8 139.0166 C3H8O4P 0.4 Phosphoric acid 3 4.0 89.0244 C3H5O3 0.1 4 4.2 75.0088 C2H3O3 -‐0.2 Methyl Carbonate 5 5.3 139.0071 C3H7O4S 0.4 Propyl sulfate 6 6.2 112.9810 CH3O3FP 0.3 Methyl Phosphorofluoridate 7 7.1 126.9966 C2H5O3FP 0.1 Ethyl phosphorofluoridate 8 8.2 123.0122 C3H7O3S 0.3 Propyl sulfonate 9 9.8 140.9864 C2H5O5S 0.3 2-‐hydroxyethyl sulfate 10 10.0 155.0020 C3H7O5S -‐0.3 11 14.2 140.9958 C2H6O5P 0.1 2-‐hydroxyethyl hydrogen phosphate 12 14.3 125.0009 C2H6O4P -‐0.1 ethyl hydrogen phosphate 13 14.4 110.9853 CH4O4P -‐0.2 methyl hydrogenphosphate 14 15.3 131.0350 C5H7O4 0 3-‐carboxy-‐2-‐methylpropanoate 15 15.6 117.0193 C4H5O4 0.2 methyl malonate 16 15.7 133.0143 C4H5O5 0.2 3-‐carboxy-‐3-‐hydroxypropanoate 17 15.9 117.0194 C4H5O4 0.2 Succinate 18 16.2 103.0037 C3H3O4 0.3 2-‐carboxyacetate 19 16.6 98.9653 HO3FP 0 hydrogen phosphorofluoridate 20 17.1 118.9986 C3H3O5 21 17.2 96.9601 HO4S -‐0.2 hydrogen sulfate 22 23.0 96.9696 H2O4P -‐0.5 dihydrogen phosphate 23 24.2 204.9674 C2H7O7P2 0.7 hydrogen (1-‐hydroxy-‐1-‐phosphono-‐ethyl)-‐phosphonate 24 24.4 190.9517 CH5O7P2 1.1 Methyl trihydrogen diphosphate 25 26.1 131.0349 C5H7O4 -‐0.4 26 26.7 175.0249 C6H7O6 0.3 27 26.9 147.0299 C5H7O5 0.3 4-‐carboxy-‐3-‐hydroxybutanoate 28 27.8 161.0092 C5H5O6 0.1 Ethanetricarboxylate 29 27.9 103.0037 C3H3O4 0 30 41.7 176.9360 H3O7P2 0.3 Trihydrogen diphosphate 31 49.2 175.0249 C6H7O6 0.3 Tricarballyllate 32 49.8 204.9312 C6H5O8 0.1



41

Cycle Aged 45% Loss in Capacity


RT: 0.0 - 55.0 SM: 5G

0 5 10 15 20 25 30 35 40 45 50 55Time (min)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

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8.5

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9.5

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23.0

14.2

5.34.2

16.2

27.73.6 15.5 27.88.1

9.83.3

49.87.026.7

18.0 24.2 49.224.313.9 41.810.6 53.318.3



1

2

4

5 6

8 9

3

18

19

21

10

12, 13, 14

15, 16, 17

20

7

22

11 23 24

25

26

27

29

28

30

31 32

33

34

42

Component Identified from Cycle Aged 45% Loss in Capacity Components IdenPfied in Cycle Aged

Peak # RT (min) m/z (-‐) Measured

m/z (-‐) Calculated

Delta ppm Formula (-‐) Name (Based on MS results)*

1 3.2 To 3.6

125.0009 155.0116 169.0272 185.0222

125.0009 155.0115 169.0271 185.0220

0 0.6 0.6 0.6


Phosphate Esters

2 3.9 139.0166 139.0166 0.4 C3H8O4P Phosphoric acid 3 4.2 75.0088 75.0088 -‐0.2 C2H3O3 Methyl Carbonate 4 5.3 139.0071 139.0071 0 C3H7O4S Propyl sulfate 5 6.2 112.9810 112.9809 0.2 CH3O3FP Methyl Phosphorofluoridate 6 7.0 126.9966 126.9966 0.1 C2H5O3FP Ethyl Phosphorofluoridate 7 7.4 120.9965 120.9965 -‐0.1 C3H5O3S 2-‐Propene-‐1-‐sulfonic acid 8 8.2 123.0122 123.0121 0.2 C3H7O3S Propyl sulfonate 9 9.8 140.9864 140.9863 0.3 C2H5O5S 2-‐hydroxyethyl sulfate 10 10.7 110.9757 110.9758 -‐0.3 CH3O4S methyl sulfate 11 11.1 124.9914 124.9914 0.1 C2H5O4S Ethyl sulfate 12 14.2 140.9958 140.9958 0.1 C2H6O5P 2-‐hydroxyethyl hydrogen phosphate 13 14.3 125.0009 125.0009 -‐0.1 C2H6O4P ethyl hydrogen phosphate 14 14.4 110.9853 110.9853 0 CH4O4P methyl hydrogenphosphate 15 15.3 131.0350 131.0350 0 C5H7O4 3-‐carboxy-‐2-‐methylpropanoate 16 15.5 117.0193 117.0193 0.2 C4H5O4 methyl malonate 17 15.7 133.0143 133.0143 0.2 C4H5O5 3-‐carboxy-‐3-‐hydroxypropanoate 18 15.9 117.0194 117.0194 0.2 C4H5O4 Succinate 19 16.2 103.0037 103.0037 0.3 C3H3O4 2-‐carboxyacetate 20 16.6 98.9653 98.9653 0 HO3FP hydrogen phosphorofluoridate 21 17.2 96.9601 96.9601 -‐0.2 HO4S hydrogen sulfate 22 23.00 96.9696 96.9696 -‐0.5 H2O4P dihydrogen phosphate 23 24.1 204.9674 204.9674 0.7 C2H7O7P2 hydrogen (1-‐hydroxy-‐1-‐phosphono-‐ethyl)-‐phosphonate 24 24.3 190.9517 190.9517 1.1 CH5O7P2 Methyl trihydrogen diphosphate 25 24.7 218.9639 218.9639 0.2 C3H7O7S2 2-‐hydroxy-‐3-‐sulfopropane-‐1-‐sulfonate 26 26.1 175.0249 175.0249 0.5 C6H7O6 Ascorbate 27 26.7 175.0249 175.0249 0.3 C6H7O6 28 26.9 147.0299 147.0299 0.3 C5H7O5 4-‐carboxy-‐3-‐hydroxybutanoate 29 27.7 161.0092 161.0092 0 C5H5O6 Ethanetricarboxylate 30 27.8 103.0037 103.0037 0 C3H3O4 31 41.8 176.9360 176.9360 0.3 H3O7P2 trihydrogen diphosphate 32 49.2 175.0249 175.0249 0.3 C6H7O6 tricarballylate 33 49.8 204.9990 204.9990 0 C6H5O8 34 53.3 224.9312 224.9312 0. HO3F6P2 F5P-‐PO3H2F



43

Summary

•  Ion chromatography coupled with the Orbitrap Q Exactive

mass spectrometer provides a powerful platform for Li-ion battery anode impurity and degradant analysis.

• The HRAM full scan and ms/ms data with polarity switching allows for unambiguous ionic species identification and structure characterization.

• This IC-HR/AM MS-based platform provides comprehensive results which can be used for QA/QC for Lithium-ion battery manufacturers and performance evaluations.

44

IC-ICP-MS, 55Mn

•  Amount of irreversibly formed Mn species is correlated to aging

Zheng, H.; Sun, Q.; Liu, G.; Song, X.; Battaglia, V.S. Correlation between Dissolution Behavior and Electrochemical Cycling Performance for LiNi1/3Co1/3Mn1/3O2-Based Cells. J. Power Sources 2012, 207, 134–140.

45

MnxOyz-

Mn2+

Cycle- or Calendar-Aged

LiB

H+

Mn2+

Cathode Anode

Anion Analysis of Cathode Dissolution

LiNi0.42Mn0.42Co0.16O2

Mechanistic Pathway

-Mn3+

Mn4+ +

Anode* Cathode**

* Mn2+ sol .in electrolyte, migrates to anode ** Mn4+ insol .in electolyte, remains on cathode

Manganese IC-ICP-MS Analysis of Aged Li-ion Batteries

Acid-Catalyzed Dissolution of Mn to Mn3+

and Disproportionation to Mn2+ and Mn4+

46

Permanganate/Manganate Configurations

Manganate(VI) Permanganate(VII)

47

Control Anode and Calendar-Aged Anode Sample

Anion Analysis Chromatographic Conditions: Column: Dionex IonPac AS11, 2 × 250 mm Eluent: 1 mM KOH 0–5 minutes,1–30 mM KOH 5–25 minutes Eluent Source: Dionex EGC 500 KOH Cartridge Flow Rate: 0.25 mL/min Injection Volume: 2.5 µL Temperature: 30 ˚C Detection: Suppressed conductivity,

Dionex AERS 500 (2 mm) Suppressor, AutoSuppression, recycle mode

48

Manganate, Permanganate, Anion Standards, and Calendar-Aged Anode Samples

100 ppm Manganate

100 ppm Permanganate

Anion Standard

Fluoride

Chlorite Bromate

Chloride

Nitrite Sulfate

Carbonate

Bromide, Nitrate, Chlorate

0 10 20 30 -10

10

µS

Minutes

Aged Anode Sample

49

IC Anion-Exchange Analysis of Aged Li-ion Battery Samples

Summary: • Neither manganate nor permanganate are stable on the anion

exchange column

•  They may be reacting on the column and degradation products may be eluting in the vicinity of carbonate as well as earlier

•  It is possible that carbonate is produced during a reaction on the column

50

Permanganate Standard

• Positive response to direct infusion HRMS in –ESI mode • Negative response to IC-HRMS

O

Mn

O

O O

Theoretical Simulation

Experimental Result

116 117 118 119 120 121 122 123 m/z

0 20 40 60 80

100 0 20 40 60 80

100

Rel

ativ

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bund

ance

118.9181

116.9287 120.9221 118.9541 119.9219 117.9288 118.7880 115.9206 118.9183

120.9225 119.9225 122.9267 121.9267

51

Proposed Mechanism for Anionic Mn Species

•  Compound 1 formed by the reaction of permanganate with a succinic acid adduct, a plausible degradation product

•  Compound 1 degrades under acidic conditions

Tetrahedron 65 (2009) 707–739

?

52

Cycle Aged (45% Capacity Loss): IC-HRMS

•  Positive response to a Mn containing product •  Proposed Mn species consistent with a retention time of 16-33 min •  pH 10-11 of the aq anode extract •  2 decimal point m/z accuracy supports proposed species •  4 decimal point m/z accuracy disputes proposed species

Experimental m/z

Calculated m/z

234.98 234.93

Experimental m/z

Calculated m/z

234.9779 234.9281

2 Decimal Point Accuracy 4 Decimal Point Accuracy

53

IC-HRMS and Direct Infusion HRMS Analysis of Aged Li-ion Battery Samples

Conclusions: •  Permanganate Standard

•  Detected by direct infusion HRMS in –ESI mode •  Not detected by anion exchange IC-HRMS

•  Proposed Mn Oxide complex •  Positive response by IC-HRMS for aged 40% capacity loss sample •  Proposed species was disproved by direct infusion HRMS in –ESI mode with 4

decimal point accuracy •  No anionic Mn containing products observed by IC-HRMS

•  Next Steps •  Cation exchange IC with +ESI mode HRMS to validate presence of Mn2+ from

the degradation of permanganate

54

Acknowledgement

•  Chris Pohl, Thermo Fisher Scientific, Sunnyvale, CA, USA

•  Charanjit Saini, Thermo Fisher Scientific, Sunnyvale CA, USA

55

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Date post:	15-Jul-2015
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Chromatography: Analysis of Phosphate and Manganese degradation Products in Aged lithium Ion...

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